CN114456322A - Ultraviolet-curable resin composition - Google Patents

Abstract

The present invention relates to an ultraviolet light curable resin composition. The composition comprises: 5-40 parts by weight of photocurable oligomer (A); 10-50 parts by weight of vinyl resin (B); 5-40 parts by weight of unsaturated ethylenic monomer (C); and 0.1 to 15 parts by weight of photopolymerization initiator (D); wherein, photocurable oligomer (A) + vinyl resin (B) + unsaturated ethylenic monomer (C) = 100 parts by weight, and vinyl Resin (B) is formed by polymerizing the following monomers: aromatic compound monomers or aliphatic monomers (B1), wherein the aromatic compound monomers include C8-C12 monovinyl aromatic compounds or their halogenated derivatives; and The 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. The UV-curable resin of the present invention can provide good adhesion to metals.

Description

UV curable resin composition

technical field

The present invention relates to the field of polymer resins and coatings, and particularly relates to a composition of an ultraviolet curable resin suitable for coatings.

Background technique

UV curing technology is a green technology developed in the 1970s. Its advantages are that the process can reduce energy waste, increase cross-linking density, shorten process time, easy to control quality, and improve production efficiency and yield. The required equipment space is small. According to the composition and hardening method of the resin, UV-curable resin conforms to the four principles of green chemistry: (1) no or a small amount of solvent can be used to meet the needs of low volatile organic compounds (VOC); (2) chemical reaction The product is non-toxic and environmentally friendly; (3) the energy utilization rate is high; (4) the reaction can be carried out at normal temperature and normal pressure. With the characteristics of different UV lamps and various UV-curable resins, we can upgrade UV-curing technology into a fast and efficient production process.

Generally, the composition formula of UV-curable resin can be divided into three parts. The first part is oligomer, which requires low viscosity, no odor, fast curing speed and low toxicity; the second part is reactive dilution monomer. Reactive Monomer, which requires properties with photoreactivity, good hardening rate, good solvent power, and low volatility; the third part is Photoinitiator, which requires properties (1) that can attract ultraviolet radiation Can and can induce polymerization; (2) good thermal stability; other additives can be added or a small amount of solvent can be added according to the performance requirements. At present, UV curing technology is widely used in major industries such as: home appliances, automobile industry, electronic industry 3C supplies, etc.

At present, UV-curable resins can only adhere to specific substrates. Most of the substrates that UV-curable coatings can adhere to are mostly organic polymer plastics; products that can meet inorganic materials such as metal or ceramic or glass substrates are relatively Fewer products, which can meet the adhesion of various general types of substrates at the same time (such as engineering plastics, metal substrates, glass, ceramics or composite materials and other substrates). Therefore, although the existing UV-curable resins generally meet the requirements, they are not completely satisfactory, and further improvements are still needed in the industry.

SUMMARY OF THE INVENTION

The purpose of the present invention is to disclose a composition of ultraviolet curable resin for coating; the composition of ultraviolet light coating can satisfy the interlayer adhesion of different types of substrates at the same time after being irradiated with ultraviolet light; Molecular plastic substrates and inorganic glass substrates or the above-mentioned composite material substrates, etc. This composition also has the advantages of good film leveling, recoating, and vapor deposition.

In order to achieve the above purpose of the invention, the research and development team of the present invention, after a lot of research and reading literature materials, has continuously innovated thinking and repeatedly tried polymer synthesis and formula adjustment, and obtained a product with the advantages of adhesion, wide application, leveling, recoatability, etc. composition of UV-curable coatings.

The invention provides an ultraviolet curable resin composition, comprising: 5-40 parts by weight of a photocurable oligomer (A); 10-50 parts by weight of a vinyl resin (B); 5-40 parts by weight of a non-ferrous resin Saturated ethylenic monomer (C); and 0.1-15 parts by weight of photopolymerization initiator (D); wherein, photocurable oligomer (A) + vinyl resin (B) + unsaturated ethylenic monomer ( C)=100 parts by weight, and the vinyl resin (B) is formed by the polymerization of the following monomers: aromatic compound monomers or aliphatic monomers (B1), wherein the aromatic compound monomers include C8-C12 monovinyl aromatic compounds family compound or its halogenated derivative; and dibasic acid monomer (B2); wherein, the mole ratio of aromatic compound monomer or aliphatic monomer (B1) to dibasic acid monomer (B2) is 10～ 20.

Detailed ways

In order to make the features of the present disclosure clear and easy to understand, the following specific examples are given, and the detailed description is as follows. For other precautions, please refer to the technical field.

The following is a detailed description of the ultraviolet curable resin composition provided by the present invention.

In the context, the terms "about", "approximately" and "substantially" generally mean within 5%, preferably within 3%, more preferably within 1%, or within 2% of a given value or range. within 1%, or within 0.5%. The quantity given here is an approximate quantity, that is, "about", "approximately", "substantially" can still be implied without the specific description of "about", "approximately", "substantially" meaning.

In this specification, a range represented by "one numerical value to another numerical value" is a general expression that avoids enumerating all the numerical values in the range in the specification. Therefore, unless there is a special additional description or a clear departure from the reasonable common knowledge in the art, reciting a specific numerical range in the present invention is equivalent to disclosing any numerical value within the numerical range and any numerical value within the numerical range. A smaller numerical range defined by an arbitrary numerical value (including an integer and a numerical value rounded to one decimal place) is the same as if the arbitrary numerical value and the smaller numerical range are explicitly written in the specification. For example, when only "1 to 10" is described in the description, it may be equivalent to disclose the ranges of "3 to 5" and "2.5-6.8", regardless of whether other numerical values are listed in the specification.

In this specification, "aromatic compounds" refer to benzene or its derivatives, hydrocarbon compounds having one or more benzene rings in its molecular structure, and aromatic compounds such as benzene, toluene, ethylbenzene, isobutylbenzene, But it is not limited to this. "Aromatic halogenated compound" means that one or more hydrogen atoms in the aromatic compound are replaced by halogen atoms (fluorine, chlorine, bromine, iodine). Styrene, but not limited to this. "Dibasic acid" refers to a hydrocarbon compound having two carboxyl (-COOH) functional groups, such as, but not limited to, formalin acid and maleic acid. "Alkylene" refers to a chain organic functional group containing two atoms of carbon and hydrogen, which can be represented as -C _n H _2n -, and both ends of the chain can be connected to other groups. In some embodiments, the alkylene group may include, but not limited to, methylidene, ethylidene, propylidene, and butylene. "Alkenylene" refers to an organic functional group containing a carbon-carbon double bond, and both ends of the chain can be connected to other groups. In some embodiments, the alkenylene group may include, but not limited to, vinylene, propenylene, and butenylene.

An embodiment of the present invention provides a UV-curable resin composition; the UV-curable resin composition can be adhered to a metal substrate, a plastic substrate, a glass substrate or the above-mentioned composite materials after being cured by ultraviolet light Substrate, etc., and finally achieve the purpose of protecting the substrate and being decorative. The UV curable resin composition for coating disclosed in the invention has good substrate adhesion, wide applicability and processability, and can be suitable for the application of primer coating and top coating in the coating field.

In detail, the ultraviolet curable resin composition of the embodiment of the present invention comprises:

5-40 parts by weight of photocurable oligomer (A);

10-50 parts by weight of vinyl resin (B);

5-40 parts by weight of unsaturated ethylenic monomer (C); and

0.1 to 15 parts by weight of a photopolymerization initiator (D);

Wherein, photocurable oligomer (A)+vinyl resin (B)+unsaturated ethylenic monomer (C)=100 parts by weight, and vinyl resin (B) is formed by polymerizing the following monomers:

Aromatic compound monomers or aliphatic monomers (B1), wherein the aromatic compound monomers include C8-C12 monovinyl aromatic compounds or halogenated derivatives thereof; and

Dibasic acid monomer (B2)

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 organic materials and inorganic materials at the same time.

At present, UV-curable resins can only adhere to specific substrates. Most of the substrates that UV-curable coatings can adhere to are mostly organic polymer plastics; products that can meet inorganic materials such as metal or ceramic or glass substrates are relatively Fewer products, which can meet the adhesion of various general types of substrates at the same time (such as engineering plastics, metal substrates, glass, ceramics or composite materials and other substrates). Therefore, in the embodiments of the present invention, by using dibasic acid monomers to polymerize into vinyl resins, the adhesion of the UV-curable resin composition to the metal substrate can be provided. In addition, organosiloxane may be added as necessary to improve the adhesion of the ultraviolet curable resin composition to metal substrates and glass substrates.

In the present invention, it is defined that the photocurable oligomer (A)+vinyl resin (B)+unsaturated ethylenic monomer (C)=100 parts by weight.

The following will give a detailed description of each component in the UV-curable resin composition:

[(A) Photocurable oligomer]

According to some embodiments of the present invention, the photocurable oligomer (A) has two or more unsaturated ethylenic bonds, including but not limited to: urethane acrylic oligomer, polyacrylic acid oligomer, polyester oligomer, Polyether oligomers, epoxy resin oligomers or the aforementioned compositions, preferably polyurethane acrylic oligomers. The photocurable oligomer can help the coating to generate bridging and crosslinking after photocuring, so as to achieve the purpose of improving the basic hardness, weather resistance and chemical resistance of the coating.

According to some embodiments of the present invention, the weight average molecular weight of the photocurable oligomer (A) is between 1000 and 10,000, preferably between 2000 and 8,000.

According to some embodiments of the present invention, the content of the photocurable oligomer (A) is preferably 5-40 parts by weight.

According to the inventor's research, in some embodiments, if the content of the photocurable oligomer (A) is more than 40 parts, the bridging density will be too high, resulting in excessive shrinkage of the coating, resulting in poor adhesion or coating turtles. cracks, etc. If the content of the photocurable oligomer (A) is less than 5 parts, problems such as insufficient physical properties of the coating, poor chemical resistance and poor water resistance are easily caused due to the too low bridging density.

[(B) Vinyl Resin]

Vinyl resin can be used to control the brittleness and viscosity of the coating film, and can provide good adhesion to the substrate.

In some embodiments, the weight average molecular weight of vinyl resin (B) is between 5,000 and 200,000.

According to the inventor's research, in some embodiments, if the weight-average molecular weight of the vinyl resin (B) is lower than 5,000, the adhesion effect will be poor due to the brittleness of the coating film. If the weight-average molecular weight of the vinyl resin (B) is higher than 200,000, the system viscosity will be too high, which will lead to difficult construction and adversely affect the coating film performance in practical use.

According to some embodiments of the present invention, the content of vinyl resin (B) is preferably 10-50 parts by weight, more preferably 20-40 parts by weight.

In some embodiments, the vinyl resin (B) is formed by the polymerization of the following monomers: aromatic compound monomers or aliphatic monomers (B1), dibasic acid monomers (B2).

[(B1) Aromatic compound monomer or aliphatic monomer]

In some embodiments, aromatic compound monomers, including C8-C12 monovinyl aromatic compounds or halogenated derivatives thereof, can be exemplified by styrene, α-methyl vinyl benzene, vinyl toluene, tert-butyl benzene Ethylene and chlorostyrene are not limited to these.

In some embodiments, the aromatic compound monomer preferably has the structure shown below.

wherein R1-R5 are each independently a C1-C10 alkyl group, a hydrogen atom or a halogen.

In some embodiments, the aromatic monomer is more preferably styrene, having the structure shown below.

In some embodiments, the aliphatic monomer is an alkyl acrylate or a substituted alkyl acrylate.

In some embodiments, the aliphatic monomer has the structure shown below, wherein R6 and R7 are each independently a C1-C10 alkyl group or a hydrogen atom.

In some embodiments, the aliphatic monomer is preferably a C4-C10 alkyl methacrylate monomer or a C3-C10 alkyl acrylate monomer.

In some embodiments, C4-C10 alkyl methacrylate monomers, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-methacrylate Butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-methoxyethyl methacrylate, ethoxymethyl methacrylate.

In some embodiments, the alkyl methacrylate monomer is preferably methyl methacrylate, having the structure shown below.

In some embodiments, C3-C10 alkyl acrylate monomers can be listed as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, acrylic acid Hexyl ester, 2-methoxyethyl acrylate, ethoxymethyl acrylate, but not necessarily limited to these.

In some embodiments, the alkyl acrylate monomer is preferably butyl acrylate, having the structure shown below.

In some embodiments, the mole ratio of the aromatic compound monomer or aliphatic monomer (B1) to the dibasic acid monomer (B2) is 10-20.

[(B2) Dibasic acid monomer]

Dibasic acid monomers can provide carboxyl groups to generate chelation with metals, and slightly corrode the metal surface and destroy the dense surface of the metal, so as to achieve good adhesion to the metal.

In some embodiments, the dibasic acid monomer (B2) may include maleic acid, formalin acid, citraconic acid, mesaconic acid, and itaconic acid. , 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dihydrophthalic acid Methyltetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid are not limited to these.

In some embodiments, the diacid monomer (B2) preferably has the structure shown below.

Wherein, R8 is a C1-C10 alkylene group or an alkenylene group.

In some embodiments, the diacid monomer (B2) has an ethylenically unsaturated bond.

In some embodiments, the diacid monomer (B2) is more preferably formalin or maleic acid.

In some embodiments, the diacid monomer (B2) is particularly preferably formalin acid, having the structure shown below.

According to some embodiments of the present invention, the content of the dibasic acid monomer (B2) is preferably 0.1-20 parts by weight, more preferably 1-10 parts by weight.

According to the research of the inventor, in some embodiments, if the content of the dibasic acid monomer (B2) is more than 20 parts, it will be difficult to be used as a coating because the viscosity is too high. If the content of the dibasic acid monomer (B2) is less than 0.1 part, the adhesion effect to the metal is not good.

[(C) Unsaturated ethylenic monomer]

The composition of UV curable resin with different hardness can be provided by adjusting the amount of unsaturated ethylenic monomer.

According to some embodiments of the present invention, the content of the unsaturated ethylenic monomer (C) is preferably 5-40 parts by weight, more preferably 10-35 parts by weight.

In some embodiments, the unsaturated ethylenic monomer (C) has more than one unsaturated ethylenic bond, such as 1,6-hexanediol diacrylate, propylene glycol di(meth)acrylate, di(meth)acrylate base) dipropylene glycol acrylate, propylene glycol di(meth)acrylate, tripropylene glycol diacrylate, trimethylol propane triacrylate, butylene glycol di(meth)acrylate, isopentaerythritol triacrylate, dipropylene glycol Neopentyl glycol (meth)acrylate, bis-trimethylolpropane tetraacrylate, β-(acryloyloxy)propionic acid, glycerol trihydroxypropyl ether triacrylate, tripropylene glycol diacrylate, dipropylene glycol Diacrylate, polydipentaerythritol hexaacrylate, glycerol di(meth)acrylate, isotaerythritol di(meth)acrylate, ethylene glycol glycidyl ether di(meth)acrylate, diethylene glycol diacrylate Glycidyl ether di(meth)acrylate, phthalate diglycidyl ether di(meth)acrylate, hydroxypivalic acid denatured neopentyl glycol di(meth)acrylate, (methyl) Cyclohexyl acrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, isocyanurate ethylene oxide modified di(methyl) Acrylates, Trimethylolpropane trimethacrylate, Isopentaerythritol tetra(meth)acrylate, Diisopentaerythritol tri(meth)acrylate, Diisopentaerythritol tetra(meth)acrylate Alcohol ester, Diisopentaerythritol penta(meth)acrylate, Diisopentaerythritol hexa(meth)acrylate, Tri(meth)acryloyloxyethoxytrimethylolpropane, Glycerin polyglycidol Ether poly(meth)acrylate, isocyanurate ethylene oxide modified tri(meth)acrylate, ethylene oxide modified diisopentaerythritol penta(meth)acrylate, ethylene oxide modified two Isopentaerythritol hexa(meth)acrylate, ethylene oxide-modified isopentaerythritol tri(meth)acrylate, ethylene oxide-modified isopentaerythritol tetra(meth)acrylate, succinic acid-modified iso Pentaerythritol tri(meth)acrylate is not necessarily limited to this, but 1,6-hexanediol diacrylate is preferable.

[(D) Photopolymerization Initiator]

The photopolymerization initiator can harden the ultraviolet curable resin composition by irradiating the active energy of ultraviolet rays for a very short time.

According to some embodiments of the present invention, the content of the photopolymerization initiator (D) is preferably 0.1-15 parts by weight, more preferably 1-8 parts by weight.

According to the research of the inventor, in some embodiments, for example, the content of the photopolymerization initiator (D) is greater than or equal to 8 parts, which is likely to cause a reaction after coating. If the content of the photopolymerization initiator (D) is less than 1 part, it will cause the problem that the coating cannot be cured and dried.

In some embodiments, the photopolymerization initiator (D) includes two or more different photopolymerization initiators.

In some embodiments, the photopolymerization initiator (D), such as diethoxyacetophenone, 2-hydroxy-methylphenylpropan-1-one, benzyl dimethyl ketal, 4-(2 -Hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylmethanone, 2-methyl-1-(4-methylthiophenyl)-2 -Morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-hydroxy-2-methyl-1-[4- (1-methylvinyl)phenyl]acetone, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Isopropylthioxanthone, ethyl 4-(N,N-dimethylamino)benzoate, benzophenone, 4-chlorobenzophenone, methyl o-benzoylbenzoate, diphenyl iodide Onium salt hexafluorophosphate, isooctyl para-N,N-dimethylaminobenzoate, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4 - Benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethyl benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzene tetramethylammonium bromide, (4-benzene Formylbenzyl) trimethylammonium chloride, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone , 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthene-9-one methyl chloride, 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphonate ethyl ester bis(2,6-dimethoxybenzoyl ]-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, but not necessarily limited thereto, preferably 1- Hydroxycyclohexyl phenyl ketone.

[(E) Organosiloxane Coupling Agent]

An organosiloxane coupling agent can be added as needed, and the hydroxyl group or alkoxy group of the organosiloxane can be bonded by condensation reaction with the hydroxyl group on the glass surface, thereby improving the adhesion to the glass.

According to some embodiments of the present invention, the content of the organosiloxane coupling agent (E) is 0.1-5 parts by weight, preferably 0.3-3 parts by weight.

In some embodiments, the organosiloxane coupling agent (E) includes ethylenically unsaturated bonds.

In some embodiments, the organosiloxane coupling agent (E), for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylpara(2-methoxyethoxy)silane, 3 - Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyl-trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-ring Oxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy Aminopropylethoxydimethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyl Trimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethylsilane Oxysilane, 3-methacryloyloxypropyltrimethoxysilane, and/or 3-mercaptopropyltrimethoxysilane, but not necessarily limited thereto, preferably 3-methacryloyloxypropyl oxy-trimethoxysilane.

Hereinafter, the present disclosure will provide several examples and comparative examples to more specifically illustrate the effects achieved by the ultraviolet curable resin composition according to the embodiments of the present disclosure, and the ultraviolet light-curable resin compositions prepared by applying the present disclosure. Characteristics of photocurable resin compositions. However, the following examples and comparative examples are for illustrative purposes only, and should not be construed as limitations of the present disclosure.

[Synthesis Example 1] Vinyl Resin A

In a reactor equipped with a stirrer, a temperature controller and a nitrogen blowing device, (B1) 51 g of styrene, (B4) 34.3 g of butyl acrylate, 5.7 g of hydroxyethyl methacrylate, (B3) were added in sequence. ) After mixing 6 grams of methyl methacrylate, (B2) 3 grams of formalin acid and 27.4 grams of n-butyl acetate: from room temperature, the temperature is slowly raised to 110 ° C, and then the pre-mixed di-tert-butyl peroxide 2 grams and 27.4 grams of n-butyl acetate are slowly dropped into the reactor, the titration time is controlled to be completed within 3 hours, and the temperature is lowered after 8 hours of continuous heating, and a transparent and viscous vinyl resin can be obtained at this time; The theoretical solids content is about 65%.

[Synthesis Example 2] Vinyl Resin B

In a reactor equipped with a stirrer, a temperature controller and a nitrogen blowing device, (B1) 54 g of styrene, (B4) 31.5 g of butyl acrylate, 5.5 g of hydroxyethyl methacrylate, (B3) were added in sequence. ) After mixing 6 grams of methyl methacrylate, 3 grams of (B2) maleic acid and 27.4 grams of n-butyl acetate: start slowly warming up to 110°C from room temperature, then mix 2 grams of pre-mixed di-tert-butyl peroxide After 27.3 grams of n-butyl acetate and n-butyl acetate are slowly dropped into the reactor, the titration time is controlled to be completed within 3 hours, and the temperature is started after heating for 8 hours, and a transparent and viscous vinyl resin can be obtained at this time; The solids content is about 65%.

[Synthesis Example 3] Vinyl Resin C

In a reactor equipped with a stirrer, a temperature controller and a nitrogen blowing device, (B1) 51 g of styrene, (B4) 34.2 g of butyl acrylate, 8.8 g of hydroxyethyl methacrylate, (B3) were added in sequence ) After mixing 6 grams of methyl methacrylate and 27.4 grams of n-butyl acetate: from room temperature, the temperature is slowly raised to 110 ° C, then the pre-mixed 2 grams of di-tert-butyl peroxide and 27.4 grams of n-butyl acetate are slowly Into the reaction kettle, the titration time is controlled to be completed within 3 hours, and the temperature is started after heating for 8 hours, and a transparent and viscous vinyl resin can be obtained at this time; The theoretical solid content is about 65%.

[Example 1] Composition of UV coating

Take 22.9 grams of (B) vinyl resin Vinyl resin A in Example 1; (A) 6.9 grams of polyurethane acrylic oligomer UB-63026 (manufacturer: China Taiwan Lida Chemical Co., Ltd.); reaction monomer ( C) Trimethylolpropane propoxy (3) triacrylate (TMP3POTA) 4.6 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); reaction monomer (C) 1,6-hexanediol diacrylic acid Ester (1,6HDDA) 2.3 g (manufacturer: China Taiwan Guojing Chemical Co., Ltd.); (D) photoinitiator Irgacure 184 1.4 g (manufacturer: German business BASF Co., Ltd.); finally added solvent ethyl acetate After mixing 31 grams of ester and 31 grams of n-butyl acetate uniformly, a coating solution with a solid content of 30% can be obtained.

[Example 2] Composition of UV coating

Take 23.5 grams of (B) vinyl resin Vinyl resin B in Example 1; (A) 4.7 grams of polyurethane acrylic oligomer UB-63026 (manufacturer: China Taiwan Lida Chemical Co., Ltd.); reaction monomer ( C) Trimethylolpropane propoxy (3) triacrylate (TMP3POTA) 3.5 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); reaction monomer (C) 1,6-hexanediol diacrylic acid Ester (1,6HDDA) 3.5 g (manufacturer: China Taiwan Guojing Chemical Co., Ltd.); (D) photoinitiator Irgacure 184 1.4 g (manufacturer: German business BASF Co., Ltd.); finally add solvent ethyl acetate After mixing 31.7 grams of ester and 31.7 grams of n-butyl acetate uniformly, a coating liquid with a solid content of 30% can be obtained.

[Example 3] Composition of UV coating

Take 23.7 grams of (B) vinyl resin Vinyl resin C in Example 1; (A) 4.7 grams of polyurethane acrylic oligomer UB-63026 (manufacturer: China Taiwan Lida Chemical Co., Ltd.); reaction monomer ( C) Trimethylolpropane propoxy (3) triacrylate (TMP3POTA) 3.6 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); reaction monomer (C) 1,6-hexanediol diacrylic acid Ester (1,6HDDA) 2.4 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); (E) Organosiloxane, 3-methacryloyloxypropyl-trimethoxysilane (KBM-503) 0.3 g (manufacturer: Shin-Etsu Chemical Co., Ltd., Japan); (D) photoinitiator Irgacure 184 1.4 g (manufacturer: BASF AG, Germany); finally add solvent ethyl acetate 32 g and n-butyl acetate 32 g After mixing uniformly, a coating liquid with a solid content of 30% can be obtained.

[Comparative Example 1] Composition of UV coating

Take 22.9 grams of (B) vinyl resin Vinyl resin C in Example 1; (A) 6.9 grams of polyurethane acrylic oligomer UB-63026 (manufacturer: China Taiwan Lida Chemical Co., Ltd.); reaction monomer ( C) Trimethylolpropane propoxy (3) triacrylate (TMP3POTA) 4.6 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); reaction monomer (C) 1,6-hexanediol diacrylic acid Ester (1,6HDDA) 2.3 g (manufacturer: China Taiwan Guojing Chemical Co., Ltd.); (D) photoinitiator Irgacure 184 1.4 g (manufacturer: German business BASF Co., Ltd.); finally added solvent ethyl acetate After mixing 31 grams of ester and 31 grams of n-butyl acetate uniformly, a coating solution with a solid content of 30% can be obtained.

[Comparative Example 2] Composition of UV coating

Take 22.9 grams of (B) vinyl resin Vinyl resin C in Example 1; (A) 2.3 grams of polyurethane acrylic oligomer UB-63026 (manufacturer: China Taiwan Lida Chemical Co., Ltd.) reaction monomer (C ) Trimethylolpropane propoxy (3) triacrylate (TMP3POTA) 6.9 g (manufacturer: China Taiwan Guojing Chemical Co., Ltd.); reaction monomer (C) 1,6-hexanediol diacrylate (1,6HDDA) 4.6 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); (E) organosiloxane, 3-methacryloyloxypropyl-trimethoxysilane (KBM-503) 0.3 g (Manufacturer: Shin-Etsu Chemical Co., Ltd., Japan); (D) Irgacure 184, a photoinitiator, 1.4 g (manufacturer: BASF, Germany); Finally, add solvent ethyl acetate 30.9 g and n-butyl acetate 30.9 g to mix After uniformity, a coating liquid with a solid content of 30% can be obtained.

The polystyrene-equivalent weight average molecular weight (Mw) of the vinyl resin (B) and the photocurable oligomer (A) was measured by gel chromatography (GPC method) under the following conditions.

Device: ALLANCE e2695 (manufactured by Waters Corporation)

Column: TSK-GEL G5000HXL, TSK-GEL G4000HXL, TSK-GEL G3000HXL, TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF

Flow rate: 1.0mL/min

Concentration of detected liquid and solid content: 0.4%

Injection volume: 100 μL

Detector: RI

Calibration standard materials: 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 Corporation).

The components and weight ratios of the following examples and comparative examples are shown in Table 1.

[Table 1]

Example 1 Embodiment 2 Embodiment 3 Comparative Example 1 Comparative Example 2 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 each component are described as follows:

Vinyl Resin A: Vinyl resin (containing dibasic acid monomer) obtained in Synthesis Example 1

Vinyl Resin B: vinyl resin (diacid-containing monomer) obtained in Synthesis Example 2

Vinyl Resin C: vinyl resin obtained in Synthesis Example 3

UB-63026*: Polyurethane acrylic oligomer (Manufacturer: Taiwan Lida Chemical Co., Ltd.)

TMP3POTA: Trimethylolpropane propoxy (3) triacrylate (manufacturer: Taiwan Guojing Chemical Co., Ltd.)

1,6HDDA: 1,6-Hexanediol diacrylate (Manufacturer: Taiwan Guojing Chemical Co., Ltd.)

KBM 503: Organosiloxane, 3-methacryloyloxypropyl-trimethoxysilane (manufacturer: Shin-Etsu Chemical Co., Ltd.)

Iragcure 184: Photoinitiator (Manufacturer: BASF AG, Germany)

EAC: Ethyl acetate

BAC: n-butyl acetate

NV: The mass percentage of the remaining part of the paint after drying to the total.

[penetration test]

The test specification tested using the Nippon Denshoku NDH-5000 instrument is according to the practice described in JISK-7105; where penetration is defined as the sum of the light rays penetrating through the substrate.

[Haze test]

The test specification tested using the Nippon Denshoku NDH-5000 instrument is according to the practice described in JISK-7105; where haze is defined as the value obtained by dividing the diffused light by the transmitted light after passing through the substrate.

[Hardness Testing]

The method used in the present invention is the surface pencil hardness method, and this method is described as follows according to JIS K-5600: using the specified pencil model (Japanese Mitsubishi red pencil) different pencil models have different hardnesses, and the models are 6B, 5B, 4B , 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H represent different grades, of which 6B is the softest and 9H is the hardest. The pencil is set up on a test trolley with a unit load of 750gf/cm ² , and the pencil is pushed forward to test 5 times on the coating film in different areas; visually determine whether the film surface in the test area is damaged by the pencil. In order to pass the test, at least three areas must be completely free of scars in the five areas of the test. If the three areas cannot be passed, change to a softer pencil model and continue the test until at least three areas are free of scars. The pencil model used at this time is The pencil hardness value of this coating film (such as pencil hardness 2H or 3H, etc.).

[Table 2]

Example 1 Embodiment 2 Embodiment 3 Comparative Example 1 Comparative Example 2 Penetration 92.13 92.22 92.47 92.39 92.37 haze 0.26 0.21 0.23 0.25 0.28 hardness 2H H H 2H H

[Film Adhesion Test]

Adhesion test refers to the reference standard of the 100-grid knife test method is ASTM D-3359; the test method is described as follows:

Make 100 scratches (1x 1cm ² ) on the surface of the pre-tested coating film with a special knife of 100 grids, and stick the 3M 600 type tape on the coating surface at an angle greater than 90 degrees. Whether the coating on the membrane surface has peeled off.

[Evaluation]

According to Table 3, the adhesion of the coating film can be judged through the peeling area of the coating film surface.

[table 3]

level Evaluation Criteria 5B The edge of the score line is extremely smooth and the coating of the square grid does not have any peeling off 4B There are small pieces of coating peeling off at the intersection of the scribe lines, but the area is less than 5% 3B There are small pieces of coating falling off at the intersection of the engraved lines, but the area is small by 5% to 15% 2B There are small pieces of coating falling off at the intersection of the engraved lines, but the area is small by 15% to 35% 1B There are small pieces of coating falling off at the intersection of the engraved lines, but the area is small by 35% to 65% 0B Coating completely peeled off

Table 4 shows the adhesion between the following Examples and Comparative Examples and the substrate.

[Table 4]

Example 1 Embodiment 2 Embodiment 3 Comparative Example 1 Comparative Example 2 acrylic sheet 5B 5B 5B 5B 5B polycarbonate 5B 5B 5B 5B 5B ABS 5B 5B 5B 5B 5B PET (untreated) 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 5B 5B 5B 0B 0B steel plate 5B 5B 5B 0B 0B Magnesium Lithium Alloy 5B 5B 5B 0B 0B aluminum plate 5B 5B 5B 0B 0B Phosphate treated board 5B 5B 5B 0B 0B

It can be seen from Table 1 and Table 4 that in Examples 1 to 3, the UV curable resin is a vinyl resin formed by polymerizing a dibasic acid monomer, wherein the dibasic acid monomer provides a carboxyl group and a metal to produce a chelating effect , and slightly corrode the metal surface and destroy the dense metal surface to achieve good adhesion to the metal.

In contrast, it can be seen from Table 1 and Table 4 that the UV curable resins of Comparative Examples 1 and 2 do not contain vinyl resins formed by polymerization of dibasic acid monomers, so they have poor adhesion to metals. .

It can be seen from Table 1 and Table 4 that in Example 3, in addition to the vinyl resin formed by the polymerization of dibasic acid monomers, the UV curable resin also includes organosiloxane, hydroxyl or alkoxyl groups of organosiloxane. It can be bonded by condensation reaction with the hydroxyl group on the glass surface to provide good adhesion to glass.

In contrast, it can be seen from Table 1 and Table 4 that the UV curable resins of Examples 1 and 2 do not include organosiloxane, so their adhesion to glass is poor.

It can be seen from Table 1 and Table 4 that in Comparative Example 2, the UV-curable resin does not contain vinyl resins formed by polymerization of dibasic acid monomers, and because the acid has no effect on the hydroxyl or alkoxy groups of the organosiloxane and glass. The condensation reaction of hydroxyl groups on the surface has a catalytic effect, so the UV-curable tree does not contain vinyl resins formed by polymerization of dibasic acid monomers, and even if it includes organosiloxane, it still has poor adhesion to glass.

To sum up, the UV curable resin can provide good adhesion to metals by polymerizing the vinyl resin containing dibasic acid monomers. The UV curable resin can improve the good adhesion to metal and glass by containing vinyl resin and organosiloxane formed by polymerization of dibasic acid monomers.

It can be seen from Table 1 and Table 2 that for the photocurable oligomer and the unsaturated ethylenic monomer, the UV curable resin of Example 1 includes a higher proportion of photocurable oligomer than Examples 2 and 3. The photocurable oligomer has more than two unsaturated ethylenic bonds, so the UV curable resin after polymerization has a higher bridging density and can provide higher hardness (2H).

In contrast, it can be seen from Table 1 and Table 2 that for photocurable oligomers and unsaturated ethylenic monomers, the UV curable resins of Examples 2 and 3 include a smaller proportion of those with more than two It is a photocurable oligomer of ethylenically unsaturated bonds, so the UV curable resin after polymerization has a lower bridging density and can provide a lower hardness (H).

To sum up, by adjusting the ratio of the photocurable oligomer and the unsaturated ethylenic monomer, different hardnesses can be provided. Therefore, the UV-curable resin has adjustable hardness.

Several embodiments are summarized above so that those with ordinary knowledge in the technical field to which the present invention pertains can better understand the viewpoints of the embodiments of the present invention. Those skilled in the art to which the present invention pertains should appreciate that they can, based on the embodiments of the present invention, design or modify other processes and structures to achieve the same objectives and/or advantages of the embodiments described herein. Those with ordinary knowledge in the technical field to which the present invention pertains should also understand that such equivalent processes and structures do not depart from the spirit and scope of the present invention, and they can, without departing from the spirit and scope of the present invention, Make all kinds of changes, substitutions, and substitutions.

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]

[ chemical formula 2]

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]

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]

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]

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]

[ chemical formula 7]

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.