TWI747600B - Uv-curable resin composition - Google Patents

Abstract

A UV-curable resin composition is provided, which includes: (A) 5~40 parts by weight of a UV curable oligomer; (B) 10~50 parts by weight of a vinyl resin; (C) 5~40 parts by weight of a monomer with unsaturated olefinic bond; and (D) 0.1~15parts by weight of a photoinitiator; wherein the vinyl resin (B) is polymerized by monomers including: (B1) an aromatic monomer or an aliphatic monomer, wherein the aromatic monomer contain a C8~C12 monovinyl aromatic compound or a halogenated derivative thereof; and (B2) a bifunctional acid monomer; wherein the molar ratio of the aromatic monomer or the aliphatic monomer (B1) to the bifunctional acid monomer (B2) is 10~33.72.

Description

UV curable resin composition

The invention relates to the field of polymer resins and coatings, and in particular to a UV curable resin composition suitable for coatings.

UV curing technology is a green technology developed in the 1270s. Its advantages are that the process can reduce energy waste, increase cross-linking density, shorten process time, easy quality control, increase production efficiency and small equipment space required for output. According to the composition and hardening method of the resin, UV-curable resin meets the four principles of green chemistry: (1) No or a small amount of solvent is required to meet the needs of low volatile organic compounds (VOC) (2) The product of chemical reaction Non-toxic and environmentally friendly (3) High energy utilization rate (4) The reaction can be carried out at normal temperature and pressure. With different UV lamp characteristics and various UV curing resins, we can upgrade UV curing technology to a fast and high-efficiency 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. Degree, odorless, fast curing speed, low toxicity; the second part is the reactive diluent monomer (Reactive Monomer), which requires photoreactivity, good hardening rate, good solvent power, low volatility, etc.; The third part is the photoinitiator, which requires properties (1) can attract ultraviolet radiation energy and can induce polymerization (2) good thermal stability; others can also be used in response to performance requirements Add additives or add a small amount of solvents, etc. At present, UV curing technology is widely used in major industries such as household appliances, automobile industry, and 3C products in the electronics industry.

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 Relatively few, there are fewer products that can simultaneously meet the adhesion of various types of substrates (such as engineering plastics, metal substrates, glass, ceramics, or composite materials). Therefore, although the existing UV-curable resins generally meet the requirements, they are not completely satisfactory, and the industry still needs further improvement.

The purpose of the present invention is to disclose a UV-curable resin composition for coating; this UV-light coating composition can simultaneously meet the interlayer adhesion of different types of substrates after being irradiated with ultraviolet light, and has the ability to simultaneously adhere to metal substrates and organic substrates. Polymer plastic substrate and inorganic glass substrate or the above The composite substrate, etc. This composition also has the advantages of good film leveling, recoatability, and vapor deposition properties.

In order to achieve the above-mentioned purpose of the invention, the R&D team of the present invention, after a lot of research and reading literature, has been constantly innovative thinking, and has repeatedly tried polymer synthesis and formulation adjustments to obtain an adhesive with universality, leveling, recoatability, etc. The advantages of UV curing coating composition.

The embodiment of the present invention provides a UV curable resin composition, comprising: (A) 5-40 parts by weight of photocurable oligomer; (B) 10-50 parts by weight of vinyl resin (C) 5-40 parts by weight Parts of unsaturated ethylenic monomer; and (D) 0.1-15 parts by weight of photopolymerization initiator; wherein the vinyl resin (B) is formed by polymerization of the following monomers: (B1) aromatic compound monomer or Aliphatic monomers, among which aromatic compound monomers include C8~C12 monovinyl aromatic compounds or halogenated derivatives thereof; and (B2) dibasic acid monomers; among them, aromatic compound monomers or aliphatic monomers The molar ratio of (B1) to the dibasic acid monomer (B2) is 10 to 33.72.

In order to make the features of the present disclosure obvious and easy to understand, the following examples are specially cited, in conjunction with the accompanying drawings, and detailed descriptions are as follows. For other precautions, please refer to the technical field.

The following is a detailed description of the ultraviolet curable resin composition provided in this case.

In the text, the terms "about", "approximately", and "substantially" usually mean within 5% of a given value or range, preferably within 3%, more preferably within 1%, or within 2% Within, or within 1%, or within 0.5%. The quantity given here is an approximate quantity, that is, without specifying "about", "approximately", "substantially", it can still imply "about", "approximately", and "substantially". meaning.

In this specification, the range represented by "a value to another value" is a general way to avoid listing all the values in the range one by one in the specification. Therefore, unless there are special additional instructions or obvious violations of common knowledge in the field, recording a specific numerical range in this case is equivalent to disclosing any numerical value within the numerical range and any numerical value within the numerical range. The smaller numerical range defined by the numerical value (including the integer and the numerical value rounded to the next decimal point) is the same as the arbitrary numerical value and the smaller numerical range are written out in the specification. For example, when only "1 to 10" is recorded, it can be equivalent to disclosing the range of "3 to 5" and "2.5-6.8", regardless of whether other numerical values are listed in the description.

In this specification, "aromatic compound" refers to benzene or its derivatives, and hydrocarbon compounds with one or more benzene rings in the molecular structure. Examples of aromatic compounds include benzene, toluene, ethylbenzene, and isobutylbenzene. But it is not limited to this. "Aromatic halogenated compound" means that one or more hydrogen atoms in an aromatic compound are replaced by halogen atoms (fluorine, chlorine, bromine, iodine). Examples of aromatic halogenated compounds include chlorostyrene, bromo Styrene, but it is not limited to this. "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 carbon and hydrogen atoms, which can be expressed as -C _n H _2n -, and other groups can be connected to both ends of the chain. In some embodiments, the alkylene group can be exemplified by methylene group, ethylene group, propylene group, and butylene group, but it is not limited thereto. "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 be exemplified by an ethylene group, a propenylene group, and a butenylene group, but is not limited thereto.

The embodiment of the present invention provides an ultraviolet-curable resin composition; this ultraviolet-curable resin composition can be cured by ultraviolet light, and can be adhered to a metal substrate, a plastic substrate, a glass substrate, or the above-mentioned composite material The substrate, etc., ultimately achieve the purpose of protecting the substrate and being able to be decorated. The UV-curable resin composition for coating disclosed in the present invention has good substrate adhesion, wide-use and processability, and can be applied to the application of primer and top coating in the field of coatings.

In detail, the ultraviolet curable resin composition of the embodiment of the present invention includes: (A) 5-40 parts by weight of light-curable oligomer; (B) 10-50 parts by weight of vinyl resin; (C) 5-40 parts by weight of unsaturated ethylenic monomers; and (D) 0.1-15 parts by weight of photopolymerization initiator; among them, the vinyl resin (B) is formed by polymerization of the following monomers: (B1 ) Aromatic compound monomers or aliphatic monomers, wherein the aromatic compound monomers include C8~C12 monovinyl aromatic compounds or halogenated derivatives thereof; and (B2) dibasic acid monomers, wherein the aromatic compound monomers The molar ratio of the bulk or aliphatic monomer (B1) to the dibasic acid monomer (B2) is 10 to 33.72.

The ultraviolet curable resin composition of the present invention has a dibasic acid monomer, which 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 Relatively few, there are fewer products that can simultaneously meet the adhesion of various types of substrates (such as engineering plastics, metal substrates, glass, ceramics, or composite materials). Therefore, in the embodiment of the present invention, by polymerizing the dibasic acid monomer into a vinyl resin, the adhesion of the ultraviolet curable resin composition to the metal substrate can be provided. In addition, organosiloxane can be added as needed to improve the adhesion of the ultraviolet light-curable resin composition to the metal substrate and the glass substrate.

The following is a detailed description of each component in the ultraviolet curable resin composition:

[(A) Light-curing oligomer]

According to some embodiments of the present invention, the photocurable oligomer (A) has more than two unsaturated ethylenic bonds, including but not limited to: polyurethane acrylic oligomer, polyacrylic oligomer, polyester oligomer, The polyether oligomer, epoxy resin oligomer or the aforementioned composition is preferably a urethane acrylic oligomer. Light-curing oligomers can help the coating to produce bridging and crosslinking after light-curing, so as to achieve the purpose of improving the basic hardness, physical properties, 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 greater than 40 parts, the bridging density will be too large, resulting in excessive shrinkage of the coating, resulting in poor adhesion or coating cracks. And other issues. If the content of the photocurable oligomer (A) is less than 5 parts, the bridging density is too low, which will easily lead to problems such as insufficient physical properties of the coating, poor chemical resistance, and poor water resistance.

[(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 the 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 less than 5,000, the coating film will be brittle and hard, resulting in poor adhesion. If the weight average molecular weight of the vinyl resin (B) is higher than 200,000, the viscosity of the system will be too high, which will cause difficulty in construction and adversely affect the performance of the coating film in actual use.

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

In some embodiments, the vinyl resin (B) is formed by 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, the aromatic compound monomers include C8~C12 monovinyl aromatic compounds or halogenated derivatives thereof, such as styrene, α-methylvinylbenzene, vinyl toluene, and tert-butylbenzene. 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 compound monomer is more preferably styrene, which has the structure shown below.

In some embodiments, the aliphatic monomer is alkyl acrylate or alkyl acrylate containing substituents.

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 ester, Isobutyl methacrylate, pentyl 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, the C3~C10 alkyl acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, acrylic acid Hexyl ester, 2-methoxyethyl acrylate, and 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 molar ratio of the aromatic compound monomer or aliphatic monomer (B1) to the dibasic acid monomer (B2) is 10 to 33.72.

[(B2) Dibasic acid monomer]

The dibasic acid monomer can provide the carboxyl group to chelate with the metal, 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) can include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3 -Vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid are not limited to these.

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

Among them, R8 is a C1~C10 alkylene group or alkenylene group.

In some embodiments, the dibasic acid monomer (B2) has an unsaturated ethylenic bond.

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

In some embodiments, the dibasic acid monomer (B2) is particularly preferably formalin acid and has 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 inventor's research, in some embodiments, if the content of the dibasic acid monomer (B2) is greater than 20 parts, it will be difficult to actually use it as a coating because of the high viscosity. 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, trimethanol propane triacrylate, butylene glycol di(meth)acrylate, isoprene erythritol triacrylate, two Neopentyl glycol (meth)acrylate, bis-trimethylolpropane tetraacrylate, β-(acryloxy) propionic acid, glycerol trihydroxypropyl ether triacrylate, tripropylene glycol diacrylate, dipropylene glycol Diacrylate, polydipentaerythritol hexaacrylate, glycerol di(meth)acrylate, isopentaerythritol di(meth)acrylate, ethylene glycol glycidyl ether di(meth)acrylate, diethylene glycol two Glycidyl ether di(meth)acrylate, phthalic acid diglycidyl ether di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol di(meth)acrylate, (meth) Cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2-Phenoxyethyl ester, tris (2-hydroxyethyl) isocyanuric acid triacrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, trimethylolpropane trimethyl Acrylic esters, isoprene erythritol tetra(meth)acrylate, diisopentaerythritol tri(meth)acrylate, diisoprene tetra(meth)acrylate, diisopentaerythritol penta(meth)acrylate Pentyleneerythritol ester, diisopentaerythritol hexa(meth)acrylate, tri(meth)acryloxyethoxytrimethylolpropane, glycerol polyglycidyl ether poly(meth)acrylate, isocyanide Uric acid ethylene oxide modified tris(meth)acrylate, ethylene oxide modified diisopentaerythritol penta(meth)acrylate, ethylene oxide modified diisopentaerythritol hexa(meth)acrylate , Ethylene oxide denatured isopentaerythritol tri(meth)acrylate, ethylene oxide denatured isopentaerythritol tetra(meth)acrylate, succinic acid denatured isopentaerythritol tri(meth)acrylate, However, it is not necessarily limited to this, and 1,6-hexanediol diacrylate is preferable.

[(D) Photopolymerization initiator]

The photopolymerization initiator can harden the ultraviolet-curable resin composition by irradiation with active energy of ultraviolet light 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 inventor's research, it is shown that in some embodiments, if the content of the photopolymerization initiator (D) is greater than or equal to 8 parts, it is easy to cause a reaction after coating. If the content of the photopolymerization initiator (D) is less than 1 part, 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) includes diethoxyacetophenone, 2-hydroxy-methylphenylpropane-1-one, benzyl dimethyl ketal, 4-(2 -Hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 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-trimethylbenzyl diphenyl phosphine oxide , Isopropyl thioxanthone, ethyl 4-(N,N-dimethylamino)benzoate, benzophenone, 4-chlorobenzophenone, methyl phthalate, diphenyl Iodonium salt hexafluorophosphate, isooctyl para-N,N-dimethylaminobenzoate, 4-methylbenzophenone, methyl phthalate, 4-phenylbenzophenone , 4-Benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6- Trimethylbenzophenone, 4-Benzoyl-N,N-dimethyl-N-[2-(1-oxy-2-propenoxy)ethyl]benzene tetramethylammonium bromide, (4 -Benzylbenzyl) trimethylammonium chloride, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Xanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one methyl chloride Compound, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, 2,4,6-trimethylbenzylphenylphosphonic acid ethyl ester bis(2,6-dimethoxy Benzyl]-2,4,4-trimethyl-pentyl phosphine oxide, bis (2,4,6-trimethylbenzyl)-phenylphosphine oxide, but it is not necessarily limited to this, but is preferably 1-hydroxycyclohexyl phenyl ketone.

[(E) Organosiloxane coupling agent]

An organosiloxane coupling agent can be added as needed. The hydroxyl or alkoxy group of the organosiloxane can be bonded by condensation reaction with the hydroxyl group on the surface of the glass to improve the 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) includes unsaturated ethylenic bonds.

In some embodiments, the organosiloxane coupling agent (E) includes vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-ring (Oxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, 3-glycidoxy propyl triethoxy silane, 3-glycidoxy propylene Propyl ethoxy dimethyl silane, 3-aminopropyl trimethoxy silane, 3-amino propyl triethoxy silane, N-(2-aminoethyl)-3-amino propyl Trimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethyl Oxysilane, 3-methacryloxypropyltrimethoxysilane, and/or 3-mercaptopropyltrimethoxysilane, but not necessarily Limited to this, 3-methacryloxypropyl-trimethoxysilane is preferable.

Hereinafter, the present disclosure will provide several embodiments and comparative examples to more specifically explain the achievable effects of the ultraviolet curable resin composition according to the embodiments of the present disclosure, and the ultraviolet light obtained by applying the present disclosure. Characteristics of photocurable resin composition. However, the following examples and comparative examples are for illustrative purposes only, and should not be interpreted as limitations to the implementation of this disclosure.

[Synthesis Example 1] Vinyl Resin A (Vinyl Resin A)

In a reactor equipped with a stirrer, a temperature controller, and a nitrogen blowing device were added (B1) 51 grams of styrene, (B4) 34.3 grams of butyl acrylate, 5.7 grams of hydroxyethyl methacrylate, (B3) ) 6 grams of methyl methacrylate, (B2) 3 grams of formalin and 27.4 grams of n-butyl acetate. After mixing: start slowly from room temperature to 110°C, and then add the pre-mixed di-tert-butyl peroxide 2 Gram and 27.4 grams of n-butyl acetate were slowly dropped into the reaction kettle. The titration time was controlled within 3 hours. After heating for 8 hours, the temperature began to decrease. At this time, a transparent and viscous vinyl resin can be obtained; The solid 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 were added (B1) 54 grams of styrene, (B4) 31.5 grams of butyl acrylate, 5.5 grams of hydroxyethyl methacrylate, (B3) ) After mixing 6 grams of methyl methacrylate, (B2) 3 grams of maleic acid and 27.4 grams of n-butyl acetate: Start slowly from room temperature to 110°C, then add 2 g of pre-mixed di-tert-butyl peroxide and 27.3 g of n-butyl acetate and slowly drop them into the reaction kettle. The titration time is controlled to be completed within 3 hours. After heating for 8 hours, the temperature will start to cool down. At this time, a transparent and viscous vinyl resin can be obtained; the theoretical solid content is about 65%.

[Synthesis Example 3] Vinyl Resin C (Vinyl Resin C)

In a reactor equipped with a stirrer, a temperature controller, and a nitrogen blowing device were added (B1) 51 grams of styrene, (B4) 34.2 grams of butyl acrylate, 8.8 grams of hydroxyethyl methacrylate, (B3) ) After mixing 6 grams of methyl methacrylate and 27.4 grams of n-butyl acetate: start slowly from room temperature to 110°C, and then mix 2 grams of pre-mixed di-tert-butyl peroxide and 27.4 grams of n-butyl acetate. Slowly drip into the reaction kettle, control the titration time to complete within 3 hours, and continue to heat for 8 hours before starting to cool down. At this time, a transparent viscous vinyl resin can be obtained; the theoretical solid content is about 65%.

[Example 1] Composition of UV coating

Take 22.9 grams of (B) Vinyl resin A in Example 1; (A) 6.9 grams of polyurethane acrylic oligomer UB-63026 (manufacturer: Taiwan Lida Chemical Co., Ltd.) Reactive monomer (C) Trimethylolpropane propoxy (3) triacrylate (TMP3POTA) 4.6 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); reaction monomer (C) 1,6-hexanediol diacrylate (1 , 6 HDDA) 2.3 grams (manufacturer: Taiwan Guojing Chemical Co., Ltd.); (D) photoinitiator Irgacure 184 1.4 grams (manufacturer: German BASF Co., Ltd.); finally add 31 grams of solvent ethyl acetate and 31 grams of n-butyl acetate and mix well to obtain a coating solution with a solid content of 30%.

[Example 2] Composition of UV coating

Take Example 1 (B) Vinyl resin B 23.5; (A) Polyurethane acrylic oligomer UB-63026 4.7 g (manufacturer: Taiwan Lida Chemical Co., Ltd.) Reactive monomer (C) III Methylolpropane propoxy (3) triacrylate (TMP3POTA) 3.5 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); reaction monomer (C) 1,6-hexanediol diacrylate (1, 6 HDDA) 3.5 grams (manufacturer: Taiwan Guojing Chemical Co., Ltd.); (D) photoinitiator Irgacure 184 1.4 grams (manufacturer: German BASF Co., Ltd.); finally add 31.7 grams of solvent ethyl acetate and After 31.7 grams of n-butyl acetate are mixed uniformly, a coating solution with a solid content of 30% can be obtained.

[Example 3] Composition of UV coating

Take 23.7 grams of (B) Vinyl resin C in Example 1; (A) 4.7 grams of polyurethane acrylic oligomer UB-63026 (manufacturer: Taiwan Lida Chemical Co., Ltd.) reactive monomer (C) Trimethylolpropane propoxy (3) triacrylate (TMP3POTA) 3.6 g (manufacturer: Taiwan Guojing Chemical Co., Ltd.); reaction monomer (C) 1,6-hexanediol diacrylate (1 , 6 HDDA) 2.4 grams (manufacturer: Taiwan Guojing Chemical Co., Ltd.); (E) organosiloxane, 3-methacryloxypropyl-trimethoxysilane (KBM-503) 0.3 grams (manufacturing Manufacturer: Shin-Etsu Chemical Co., Ltd.); (D) photoinitiator Irgacure 184 1.4 g (manufacturer: BASF, Germany) Co., Ltd.); Finally, add 32 grams of solvent ethyl acetate and 32 grams of n-butyl acetate and mix well to obtain a coating solution with a solid content of 30%.

[Comparative Example 1] Composition of UV Coating

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

[Comparative example two] UV coating composition

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

The measurement of the weight average molecular weight (Mw) in terms of polystyrene of the vinyl resin (B) and the photocurable oligomer (A) was performed 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-GEL G2000HXL

Column temperature: 40℃

Solvent: THF

Flow rate: 1.0mL/min

Concentration of solid content of tested liquid: 0.4%

Injection volume: 100μL

Detector: RI

Standard materials for calibration: 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 ingredients and weight ratios of the following examples and comparative examples are shown in Table 1.

[Table 1]

In Table 1, the compounds represented by each component are described as follows:

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

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

Vinyl Resin C: Vinyl resin UB-63026* obtained in Synthesis Example 3: Polyurethane acrylic oligomer (manufacturer: Taiwan Lida Chemical Co., Ltd.)

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

1,6 HDDA: 1,6-hexanediol diacrylate (manufacturer: Taiwan Guojing Chemical Co., Ltd.)

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

Iragcure 184: photoinitiator (manufacturer: BASF, Germany)

EAC: ethyl acetate

BAC: n-butyl acetate

[Penetration Test]

The test specifications tested using Nippon Denshoku NDH-5000 instrument are based on the method described in JISK-7105; the penetration is defined as the sum of light penetrating the substrate.

[Haze Test]

The test specifications tested using Nippon Denshoku NDH-5000 instrument are based on the method described in JISK-7105; the haze is defined as the value obtained by dividing the diffused light after passing through the substrate by the transmitted light.

[Hardness Testing]

The method used in the present invention is the surface pencil hardness method, which is described as follows according to JIS K-5600: Use the prescribed pencil model (Japan Mitsubishi red pencil). Different pencil models have different hardnesses, and the model number is 6B, 5B, 4B , 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H represent different grades, among which 6B is the softest and 9H is the hardest. The pencil is set on a ^{test vehicle with a unit load of 750gf/cm 2} and tested 5 times on the coating film in different areas by pushing the pencil forward; visually judge whether the film surface of the test area is damaged by the pencil. Test the five areas at least three areas are completely free of scars before it can be judged to pass. If the three areas cannot be passed, replace with a softer pencil model and continue the test until at least three areas are free of scars. At this time, the pencil model used is The pencil hardness value of this coating film (such as pencil hardness 2H or 3H, etc.).

[Table 2]

[Coating film adhesion test]

The adhesion test refers to the reference specification of the 100-grid knife test method as ASTM D-3359; the test method is described as follows: 100 squares of scratches (1 x 1cm ² ) are drawn on the surface of the pre-tested coating film with a 100-grid special knife, and 3M 600 After the tape is attached to the coating surface, the tape is torn off at an angle greater than 90 degrees, and then the inner eye is used to judge whether the coating on the surface of the coating film 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 4 shows the adhesion of each of the following examples and comparative examples to the substrate.

[Table 4]

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 polymerization of a dibasic acid monomer, where the dibasic acid monomer provides carboxyl group and metal chelation. , And slightly corrode the metal surface and destroy the dense surface of the metal to achieve good adhesion to the metal.

In comparison, it can be seen from Table 1 and Table 4 that the UV curable resins of Comparative Examples 1 and 2 did not contain vinyl resins formed by polymerization of dibasic acid monomers, so their adhesion to metals was not good.

It can be seen from Table 1 and Table 4 that in Example 3, the UV-curable resin not only contains vinyl resin formed by polymerization of dibasic acid monomers, but also includes organosiloxane, hydroxyl or alkoxy group of organosiloxane It can bond through the condensation reaction with the hydroxyl groups on the glass surface, providing good adhesion to the glass.

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

It can be seen from Table 1 and Table 4 that in Comparative Example 2, the UV-curable resin does not contain the vinyl resin formed by the polymerization of dibasic acid monomers. The condensation reaction of the hydroxyl groups on the surface has a catalytic effect. Therefore, the UV curable resin does not contain the vinyl resin formed by the polymerization of dibasic acid monomers. Even if it includes organosiloxanes, it still has poor adhesion to glass.

In summary, the UV-curable resin is a vinyl resin formed by polymerization of monomers containing dibasic acid, which can provide good adhesion to metals. UV-curable resin contains vinyl resin and organosiloxane formed by polymerization of dibasic acid monomer, which can improve the adhesion to metal and glass.

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

In comparison, it can be seen from Table 1 and Table 2 that for the photocurable oligomers and unsaturated ethylenic monomers, the ultraviolet curable resins of Examples 2 and 3 include a smaller proportion of Unsaturated ethylenic light-curable oligomers, so the UV-curable resin after polymerization has a lower bridging density and can provide lower hardness (H).

In summary, by adjusting the ratio of light-curable oligomers and unsaturated ethylenic monomers, different hardnesses can be provided. Therefore, UV-curable resins have adjustable hardness.

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

Claims (17)

An ultraviolet light curable resin composition, comprising: (A) 5-40 parts by weight of light-curable oligomer; (B) 10-50 parts by weight of vinyl resin; (C) 5-40 parts by weight of unsaturated Ethylenic monomer; and (D) 0.1-15 parts by weight of a photopolymerization initiator; wherein the vinyl resin (B) is formed by polymerization of the following monomers: (B1) aromatic compound monomer or aliphatic monomer Body, wherein the aromatic compound monomer includes a C8~C12 monovinyl aromatic compound or a halogenated derivative thereof; and (B2) a dibasic acid monomer; wherein the aromatic compound monomer or the aliphatic monomer The molar ratio of (B1) to the dibasic acid monomer (B2) is 10 to 33.72. The ultraviolet curable resin composition according to claim 1, wherein the aromatic compound monomer or the aliphatic monomer (B1) has the structure shown in Chemical Formula 1 or the structure shown in Chemical Formula 2, wherein R1~ R5 is each independently a C1~C10 alkyl group, a hydrogen atom or a halogen, and R6 and R7 are each independently a C1~C10 alkyl group or a hydrogen atom

[Chemical formula 2]

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 C3~C10 alkyl acrylate monomer. The ultraviolet curable resin composition according to claim 1, wherein the dibasic acid monomer (B2) has a structure as shown in Chemical Formula 3, and R8 is a C1-C10 alkylene group or alkenylene group.

The ultraviolet curable resin composition according to claim 4, wherein the dibasic acid monomer (B2) has an unsaturated ethylenic bond. The ultraviolet curable resin composition according to claim 5, wherein the dibasic acid monomer (B2) is formalin or maleic acid. The ultraviolet curable resin composition according to claim 6, wherein the dibasic acid monomer (B2) has the structure shown in Chemical Formula 4 [Chemical Formula 4]

The ultraviolet curable resin composition according to claim 4, wherein the aromatic compound monomer or the aromatic monomer in the aliphatic monomer (B1) has a structure shown in Chemical Formula 5

The ultraviolet curable resin composition according to claim 3, wherein the C4-C10 alkyl methacrylate monomer has a structure as shown in Chemical Formula 6, and the C3-C10 alkyl acrylate monomer Has the structure shown in chemical formula 7

The ultraviolet curable resin composition according to claim 1, wherein the weight average molecular weight of the vinyl resin (B) is between 5,000 and 200,000. Composition of UV-curable resin as described in claim 1 The weight average molecular weight of the photocurable oligomer (A) is between 1000 and 10,000. The ultraviolet curable resin composition according to claim 11, wherein the photocurable oligomer (A) includes a urethane acrylic oligomer, a polyacrylic oligomer, a polyester oligomer, a polyether oligomer, Epoxy resin oligomer or the aforementioned composition. The ultraviolet curable resin composition according to claim 11, wherein the photocurable oligomer (A) has two or more unsaturated ethylenic bonds. The ultraviolet curable resin composition according to claim 12, wherein the photocurable oligomer (A) is a urethane acrylic oligomer. The ultraviolet curable resin composition as described in claim 1, further comprising (E) 0.1 to 5 parts by weight of organosiloxane coupling agent. The ultraviolet curable resin composition according to claim 15, wherein the organosiloxane coupling agent includes an unsaturated ethylenic bond. The ultraviolet curable resin composition according to claim 1, wherein the photopolymerization initiator (D) includes two or more different photopolymerization initiators.