KR101771140B1 - UV-curable coating composition and high hard coating membrane using the same - Google Patents
UV-curable coating composition and high hard coating membrane using the same Download PDFInfo
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- KR101771140B1 KR101771140B1 KR1020150150976A KR20150150976A KR101771140B1 KR 101771140 B1 KR101771140 B1 KR 101771140B1 KR 1020150150976 A KR1020150150976 A KR 1020150150976A KR 20150150976 A KR20150150976 A KR 20150150976A KR 101771140 B1 KR101771140 B1 KR 101771140B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
Abstract
The present invention relates to an ultraviolet curable coating composition comprising an organosiloxane having a structure represented by the following formula (1).
[Chemical Formula 1]
(Wherein R 1 is each independently hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) aryl;
R 2 each independently represents a group selected from the group consisting of (C 1 -C 20) carboxyl, sulfonic acid, epoxy, acryl, methacryl, halogen, A vinyl group, a naphthyl group, an oxetane group and a phenyl group;
and n is an integer of 5 to 100 or less.
Description
The present invention relates to an ultraviolet ray curable coating composition and a high hardness coating film containing the same. More particularly, the present invention relates to an ultraviolet ray curable coating composition for protecting a plastic surface containing organosiloxane and having high hardness, high transparency, high adhesion and anti- The present invention relates to a high hardness coating film comprising
Hard coatings are used for surface protection of contamination-critical products such as liquid crystal displays (LCDs), plasma displays (PDPs), solar panels, light emitting displays (EL) (I.e., antifouling property), resistance to display by fingerprints, markers, etc., and / or ease of removal. The method of applying such a hard coating to the surface of a product has mainly used a method of obtaining a coating film by applying the hard coating agent thus prepared.
Conventionally, a curing method using heat has been widely used, such as Korean Patent No. 10-0845403, in order to coat and then cure a coating agent. However, the method of curing using heat is slow in production speed, and a volatile organic compound (VOC) And it is becoming more and more important for the curing method to replace them due to the environmental pollution.
Recently, a method of curing using ultraviolet (UV) has been widely used, such as Korean Patent No. 10-0961940, in which a method of replacing a method using heat is used. In the curing method using ultraviolet rays, Because it is cured, the production speed is high and solvent is used little.
As UV curing coating compounds which are widely used in the past, acrylic compounds, urethane acrylic compounds or epoxy compounds have been mainly used, but there have been problems in obtaining a coating film having weak weather resistance and chemical resistance and also having self-curing and antifouling properties .
In order to overcome the above problems, the present invention provides an ultraviolet curable coating composition for forming a coating film on the surface of a transparent plastic in order to overcome low abrasion resistance and surface hardness, .
Another object of the present invention is to provide an ultraviolet curable coating composition that is not harmful to the environment but has high transparency.
It is still another object of the present invention to provide a hard coat film containing the ultraviolet curable coating composition.
The present invention relates to a UV-curable coating composition and a high hardness coating film containing the same.
One aspect of the present invention relates to an ultraviolet curable coating composition comprising an organosiloxane having a structure represented by the following formula (1).
[Chemical Formula 1]
(Wherein R 1 is each independently hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) aryl;
R 2 each independently represents a group selected from the group consisting of (C 1 -C 20) carboxyl, sulfonic acid, epoxy, acryl, methacryl, halogen, A vinyl group, a naphthyl group, an oxetane group and a phenyl group;
and n is an integer of 5 to 100 or less.
Another aspect of the present invention relates to an ultraviolet curable coating composition wherein the organosiloxane comprises an acrylic monomer, an unsaturated ester, a slip agent, and a photoinitiator. Wherein the UV curable coating composition comprises 30 to 50% by weight of organosiloxane, 40 to 60% by weight of acrylic oligomer, 5 to 10% by weight of unsaturated polyester, 0.1 to 5% by weight of slip and 1 to 5% by weight of photoinitiator ≪ / RTI >
In the present invention, the acrylic monomer may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate , Benzyl methacrylate, methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate and benzyl acrylate Or two or more.
The unsaturated polyester may have a number average molecular weight of 1,000 to 10,000 and an acid value of 10 to 35 mg KOH / g.
In the present invention, the photoinitiator may be benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylmethane- -1-one, anisole methyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, Methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-hydroxy- 1-propanedione-2- (o-ethoxycarbonyl) -oxime, benzoin, benzyl, benzophenone, benzoylbenzoic acid, 3,3 Methyl-4-methoxybenzophenone, polyvinylbenzophenone,? -Hydroxycyclohexylbenzophenone, benzylmethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4 - dimethyl thioxanthone, isopro Thioxanthone, it may be at either or both are 2, 4-dichloro thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl tea selected from oak Santon and dodecyl silti oak Santon.
Also, in the present invention, the ultraviolet curable coating composition may further include any one or two or more additives selected from a colloid stabilizer, a slip agent, a wetting agent, a scratch agent, an antifouling agent and a UV stabilizer.
Another aspect of the present invention relates to a high hardness coating film comprising the ultraviolet curable coating composition.
The UV curable coating composition according to the present invention and the high hardness coating film containing the UV curable coating composition according to the present invention exhibit excellent properties in weather resistance, abrasion resistance and compatibility when applied to polymethyl methacrylate widely used as a high transparency plastic, Width can be maximized and can be recreated with high-functional advanced materials that can be used in electrical, electronic, engineering materials and automotive parts.
FIG. 1 is a graph showing light transmittance of a hard coating film prepared according to Examples 1 to 8 and Comparative Examples of the present invention, and is a value showing a light transmittance of a coating film according to a wavelength of an X-axis.
Hereinafter, the ultraviolet curable coating composition and the hard coat layer containing the same according to the present invention will be described in more detail with reference to specific examples. However, the following embodiments are only examples for explaining the present invention in detail, and the present invention is not limited thereto.
Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The term " siloxane " used in the present invention means a chain-like molecule having the structure of the following formula (2).
(2)
(In the above formula (2), R may be mainly hydrogen, a methyl group, a phenyl group, or an aryl group.)
When the molecules having the structure as shown in the above formula (2) are gathered to form a substance, since the individual molecules are independent, the molecular chains can freely move between each other, resulting in fluidity, in other words, liquid properties. However, the longer the molecule is, the more difficult it is to move, and the viscosity can be increased.
The UV-curable coating composition according to the present invention may comprise an organosiloxane having a structure represented by the following formula (1).
[Chemical Formula 1]
(Wherein R 1 is each independently hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) aryl;
R 2 each independently represents a group selected from the group consisting of (C 1 -C 20) carboxyl, sulfonic acid, epoxy, acryl, methacryl, halogen, A vinyl group, a naphthyl group, an oxetane group and a phenyl group;
and n is an integer of 5 to 100.)
In the synthesis of the organosiloxane represented by Formula 1, alkoxysilane and silanediol can be reacted directly under a base catalyst using a condensation reaction.
The alkoxysilane is not limited to the type as long as it is commonly used in the art for the production of siloxane compounds, and examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- ( (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, N (3,4-epoxycyclohexyl) - (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2- hydroxypropyl) -3-aminopropyltrimethoxysilane, N- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3- Triethoxysilane, 3-acryloxypropyltripropoxysilane, 3- (meth) acryloxyphenyl Peel trimethoxysilane, can be used 3- (meth) acryloxy propyl triethoxysilane and 3-a (meth) acryloxy or more either or both selected from propyltriethoxysilane propoxysilane.
The silanediol includes, for example, diphenylsilanediol, diisobutylsilanediol, silanol terminated polydimethylsiloxane, silanol terminated diphenylsiloxane-dimethylsiloxane copolymer, silanol terminated polydiphenyl Silanol terminated polydiphenylsiloxane, and silanol terminated polytrifluoropropylmethylsiloxane, and the like can be used.
When the alkoxysilane and the silanediol are polymerized, the viscosity of the siloxane resin may be controlled and a solvent may be further added for the stability of the resin. The usable solvent is not particularly limited, but alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol and butyl alcohol are preferably used.
When the alkoxysilane and silanediol are polymerized, a catalyst may be added to lower the reaction temperature and promote the polymerization reaction. The catalyst may be mainly a basic catalyst, and it is preferable to use calcium phosphate, barium hydroxide, strontium hydroxide, calcium hydroxide, calcium oxide, magnesium hydroxide magnesium oxide and the like.
It is important that the molar ratio of the alkoxysilane to the silanediol is precisely adjusted during the polymerization reaction of the organosiloxane. In this case, it is preferable to mix the alkoxysilane at a ratio of 2 molar ratio of the alkoxysilane to 3 molar ratio of the silane diol. If the ratio is out of the above range, the conversion rate may be decreased and the light transmittance may be decreased.
The ultraviolet curable coating composition according to the present invention may comprise an acrylic monomer, an unsaturated polyester, a slipping agent and a photoinitiator in an organosiloxane.
The acrylic monomer is used for imparting a stretching property to the ultraviolet curing type coating composition. Preferably, the acrylic type monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate substituted or unsubstituted aliphatic (C1-12) alkyl methacrylates such as methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; Substituted or unsubstituted substituted (C1-12) alkyl methacrylates such as cyclohexyl methacrylate; Substituted or unsubstituted aromatic (C6-12) aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; But are not limited to, methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Substituted or unsubstituted aliphatic (C1-12) alkyl acrylates such as trimethylolpropane triacrylate and the like; Substituted or unsubstituted substituted (C1-12) alkyl acrylates such as cyclohexyl acrylate; And substituted or unsubstituted aromatic (C6-12) aryl acrylates such as phenyl acrylate and benzyl acrylate, and more preferably one or more selected from the group consisting of methyl (C1-12) alkyl methacrylate such as methacrylate alone or a mixture of (C1-12) alkyl methacrylate and other acrylate monomers described above.
The above-mentioned unsaturated polyester has an effect of further improving the light transmittance and hardness of the high hardness coating film according to the present invention, and is usually obtained by polycondensation of an acid component and an alcohol component by a known method. The type of the unsaturated polyester used in the present invention is not particularly limited as long as it is known as a thermosetting or photocurable resin.
As the acid component, a polycarboxylic acid, preferably an? -Olefin-based unsaturated polycarboxylic acid, is preferably used. In particular, the? -Olefinically unsaturated polycarboxylic acid may further include maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid, and these acid components may act as anhydrides in the esterification reaction. Most preferred is maleic acid used as maleic anhydride.
The unsaturated polyester resin may further contain, as an ingredient, an additional polycarboxylic acid and a derivative thereof in addition to the? -Olefin-based unsaturated polycarboxylic acid. For example, ortho-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenehexahydrophthalic acid, dicyclopentanedicarboxylic A mixture of a resin acid addition product of an acid, a succinic acid, a glutaric acid, an adipic acid, a pimelic acid, a suberic acid, an azelaic acid, a dodecanedicarboxylic acid, a dimeric fatty acid, an acrylic acid or a maleic acid and a polycarboxylic acid .
The reaction object of the polycarboxylic acid is a polyol, preferably a diol such as ethylene glycol, propylene glycol, propane-1,3-diol; 2-methylpropane-1,3-diol; Butane-1,4-diol; Neopentyl glycol; Ethyl butyl propanediol, and other so-called neo-diols (dialkyl propane-1,3-diol, alkyl phenyl propane-1,3-diol); Hydroxypivalic acid neopentyl glycol ester (HPN), pentane-1,5-diol; 2,2,4-trimethylpentane-1,3-diol; Hexan-1, 6-diol, trimethylhexanediol, dimer diol, dimethylolcyclohexane, dimethyloltricyclodecane, perhydrobisphenol A, ethoxylated bisphenol A and the like. However, it is also possible to use higher polyfunctional polyols such as glycerol, trimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, and trishydroxyethyl isocyanurate Do.
In addition, the unsaturated polyester may contain monocarboxylic acid as a synthetic component, and these components may subsequently be located at the chain ends, since only one esterification reaction is possible. Monocarboxylic acids such as 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid and other monocarboxylic acids synthesized by the Koch or oxo method, pelargonic acid, coconut fatty acid Distillation cuts, palm kernel fatty acids and tallow or other unsaturated fatty acids, and monocarboxylic acids are commonly used with more polyfunctional polyols.
In the present invention, a mixture of these may be used. One particular embodiment uses a glycidyl ester of a saturated monocarboxylic acid, in which case glycidyl ester groups allow subsequent reaction and attachment of further compounds. In addition, the unsaturated polyester resin may comprise a hydroxycarboxylic acid and / or a derivative thereof, such as hydroxypivalic acid, dimethylolpropanoic acid, delta-valerolactone, epsilon-caprolactone, hydroxystearic acid have.
The unsaturated polyester preferably has an acid value of a number average molecular weight of 1,000 to 10,000 and 10 to 35 mg KOH / g. The desired hard coat film can be obtained in the present invention without deteriorating the workability in the range of the number average molecular weight, and it is preferable that an acid having the acid value in the above range is excellent in reactivity with a siloxane resin added together.
The slip agent is a material to be applied to the surface of the coating film during or immediately after the curing process so that the cured hard coating film can be separated from the substrate. The slip agent is lubricated by reducing the coefficient of friction, It also has the effect of promoting mixing.
The slip agent used in the present invention may be selected from primary fatty acid amides, preferably linear saturated fatty acid amides having 10 to 25 carbon atoms, and mixtures thereof. For example, cis-13 dococenoamide or erucamide, cis-9-octadecenoamide or oleamide, octadecanoylamide or stearamide, docosanoic amide or behenamide, N, N'- Stearamide, N-octadecyl-13-dococene amide, oleyl palmitamide, and the like, and more preferably behenamide or erucamide.
The photoinitiator is not particularly limited as long as it is a substance capable of effectively initiating a polymerization reaction through ultraviolet irradiation or the like in the art. Examples of the photoinitiator include acetophenone, a-ketone, photoactive oxime, benzoin, Benzophenone type, ketal type, thioxanthone type and the like can be used. Preferred examples of the benzoin ether include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2- Diphenylethan-1-one, anisole methyl ether, and the like. Examples of the acetophenone-based solvent include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 1-hydroxycyclohexylphenylketone, Hydroxy ketone, 4-phenoxydichloroacetone, 4-t-butyldichloroacetophenone, and the like. Examples of the? -ketol group include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-hydroxy-2-methylpropan- . Examples of the optically active oxime system include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like. Examples of the benzoin group include benzoin and the like. Examples of the benzyl group include benzyl and the like. Examples of the benzophenone-based compound include benzophenone, benzoylbenzoic acid, 3,3'-methyl-4-methoxybenzophenone, polyvinylbenzophenone, and? -Hydroxycyclohexylbenzophenone. Examples of the ketal group include benzylmethyl ketal and the like. Examples of the thioxanthone system include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone , 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like. The photopolymerization initiator may be used singly or in combination of two or more.
The UV curable coating composition may comprise from 30 to 50% by weight of organosiloxane, from 40 to 60% by weight of acrylic oligomer, from 5 to 10% by weight of unsaturated polyester, from 0.1 to 5% by weight of slip and from 1 to 5% by weight of photoinitiator have. Particularly, when the content of the photoinitiator is less than 1% by weight, the curing reaction does not sufficiently proceed and the desired hardness can not be obtained. When the content is more than 5% by weight, the prepared coating layer tends to be colored and the hardness may become heterogeneous.
In addition, the ultraviolet curable coating composition according to the present invention may further optionally include one or more additives selected from a colloidal stabilizer, a wetting agent, an anti-scratch agent, an antifouling agent and a UV stabilizer.
The colloidal stabilizer is used for improving the wear resistance and scratch resistance of the coating composition by further imparting surface slip property thereto, and acryloylmorpholine, dimethyl (meth) acrylamide and the like can be used, but the present invention is not limited thereto.
The ultraviolet stabilizer or ultraviolet absorber is used to improve the weatherability of the coating composition and to reduce the yellowing of the coating film with time. The ultraviolet stabilizer or the ultraviolet absorber may be used alone or in combination. In addition, wetting agents, scratching agents, and contaminants may be used alone or in combination as long as they are commonly used in the art.
The ultraviolet ray curable coating composition according to the present invention can be coated on various base plastics and photocured to produce a hard coating film. In this case, a coater commonly used in the art, such as a comma roll coater, a die roll coater, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, , It is preferable to use a bar coater.
The high hardness coating film can be appropriately adjusted depending on the properties of the base plastic and the purpose of protection, and may be formed to a thickness of, for example, 1 to 50 μm, preferably 2 to 15 μm.
The ultraviolet ray for forming the hard coat film can be appropriately controlled according to the polymerization initiator and the organosiloxane added to the composition. As the light source of ultraviolet rays, ultrahigh pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp and the like can be used. At this time, the irradiation amount of ultraviolet rays may be 250 to 1500 mJ / cm 2, more preferably 400 to 1,000 mJ / cm 2.
Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.
The physical properties of the hard coat film prepared through the following examples and comparative examples were evaluated as follows.
(Surface hardness)
The surface hardness was measured by ASTM D3502 (pencil hardness tester) method, and a pencil (MITSU-BISHI Uni wooden pencil) was used for the pencil.
(Transmittance)
The UV-VIS spectrophotometer (Mecasys, Model Optizen 2010 UV UV / VIS spectrophotometer) was used and the transmittance was measured in the range of 250 to 700 nm.
(Adhesion)
The test specimens were drawn at intervals of 2 mm to make 100 Go 's eyes and the tape was bonded. Then, the number of goggles which did not peel off of 100 goggles by pulling strongly once in the vertical direction was confirmed and shown.
(Coating film production)
A polymethylmethacrylate panel (thickness: 0.8 mm) was used as the substrate. First, the surface of the plastic was washed with isopropyl alcohol, and then the composition prepared in Examples and Comparative Examples was applied to a bar coater (RDS Corp., No. 26) was coated on one side of the substrate plastic. After coating, the coated substrate was dried at 60 ° C. for 2 minutes and irradiated for 1 minute at a light intensity of 1,000 mJ / cm 2 of ultraviolet lamp to produce a hard coating film.
(Example 1)
2.9646 g of vinyltrimethoxysilane from Aldrich, 6.4893 g of diphenylsilanediol from Aldrich was added, and the mixture was stirred for 10 minutes at 80 ° C and 400 rpm using a magnetic bar (the molar ratio was alkoxy group and hydroxy group 1: 1 molar ratio). 0.0094 g of Barium hydroxide from Aldrich was added to the above mixture, and 0.1 molar percent of the alkoxysilane functional group was added thereto. After the addition, the mixture was stirred at 80 DEG C for 4 hours. The reaction product was added to a vacuum evaporator under reduced pressure and distilled under vacuum to obtain an organosiloxane from which unreacted materials were removed.
5 g of the above organosiloxane and 5 g of a urethane acrylate (Miwon specialty chemical, MIRAMER PU-240) as an acrylic oligomer, and 2 g of methyl methacrylate as an acrylic monomer were mixed, and an α-hydroxy ketone-based iga cure 184 (3% by weight) of specialty chemicals (Irgacure 184) was added thereto and sufficiently stirred at 400 rpm for 10 minutes at room temperature to prepare an ultraviolet curable coating composition.
(Example 2)
4.967 g of 3- (trimethoxysilyl) propyl methacrylate from Aldrich, 6.4893 g of diphenylsilanediol from Aldrich was added, and the mixture was stirred for 10 minutes at 80 ° C. and 400 rpm using a magnetic bar. alkoxy group and hydroxy group were mixed at a molar ratio of 1: 1. 0.0094g of Aldrich Barium hydroxide was added to the above mixture, and barium hydroxide was added by 0.1 mole percent of the alkoxysilane functional group molar ratio. After the addition, the mixture was stirred at 80 ° C. for 4 hours. The reaction product was added to a vacuum evaporator under reduced pressure and vacuum distilled to obtain an organosiloxane from which unreacted materials had been removed. Then, an ultraviolet curing type coating composition was prepared using the same conditions and additives as in Example 1 with the organosiloxane prepared.
(Example 3)
3.4769 g of 3- (trimethoxysilyl) propyl methacrylate from Aldrich, 1.2499 g of Tetraethylorthosilicate from Aldrich, and 7.1382 g of diphenylsilanediol were mixed. In mixing, 3- (trimethoxysilyl) propyl methacrylate 7 molar ratio: 3 molar ratio of tetraethylorthosilicate: diphenylsilane diol 16.5 molar ratio. The material was placed in a flask and stirred for 10 minutes at 80 DEG C at 400 rpm using a magnetic bar.
After stirring, 0.1 g of barium hydroxide from Aldrich was added to the mixture. At this time, barium hydroxide was added by 0.1 mole percent of the functional group mole ratio of alkoxysilane. After the addition, the mixture was stirred at 80 ° C. for 4 hours. The reaction product was added to a vacuum evaporator under reduced pressure and vacuum distilled to obtain an organosiloxane from which unreacted materials had been removed. Then, an ultraviolet curing type coating composition was prepared using the same conditions and additives as in Example 1 with the organosiloxane prepared.
(Example 4)
2.4835 g of 3- (trimethoxysilyl) propyl methacrylate from Aldrich, 2.0823 g of Tetraethylorthosilicate from Aldrich, and 7.5708 g of diphenylsilanediol were mixed. 5 molar ratio of 3- (trimethoxysilyl) propyl methacrylate to tetraethylorthosilicate was mixed at a molar ratio of 5: 5 of diphenylsilane diol. The material was placed in a flask and stirred for 10 minutes at 80 DEG C at 400 rpm using a magnetic bar. After stirring, 0.0104 g of barium hydroxide from Aldrich was added to the mixture. At this time, barium hydroxide was added by 0.1 mole percent of the functional group mole ratio of alkoxysilane. After the addition, the mixture was stirred at 80 ° C. for 4 hours. The reaction product was added to a vacuum evaporator under reduced pressure and vacuum distilled to obtain an organosiloxane from which unreacted materials had been removed. Then, an ultraviolet curing type coating composition was prepared using the same conditions and additives as in Example 1 with the organosiloxane prepared.
(Example 5)
1.4901 g of 3- (trimethoxysilyl) propyl methacrylate from Aldrich, 2.9166 g of Tetraethylorthosilicate from Aldrich, and 8.0034 g of diphenylsilanediol were mixed. The mixture was mixed at a molar ratio of 3- (trimethoxysilyl) propyl methacrylate 3 molar ratio: tetraethylorthosilicate 7 molar ratio: diphenylsilane diol 18.5. The material was placed in a flask and stirred for 10 minutes at 80 DEG C at 400 rpm using a magnetic bar. After stirring, 0.0107 g of barium hydroxide from Aldrich was added to the mixture. At this time, barium hydroxide was added by 0.1 mole percent of the functional group mole ratio of alkoxysilane. After the addition, the mixture was stirred at 80 ° C. for 4 hours. The reaction product was added to a vacuum evaporator under reduced pressure and vacuum distilled to obtain an organosiloxane from which unreacted materials had been removed. Then, an ultraviolet curing type coating composition was prepared using the same conditions and additives as in Example 1 with the organosiloxane prepared.
(Example 6)
An ultraviolet curable coating composition was prepared in the same manner as in Example 2 except that only the organosiloxane was used without using urethane acrylate.
(Example 7)
An ultraviolet curable coating composition was prepared in the same manner as in Example 2, except that the content ratio of organosiloxane to urethane acrylate was changed to 7: 3.
(Example 8)
An ultraviolet curable coating composition was prepared in the same manner as in Example 2, except that the content ratio of organosiloxane to urethane acrylate was changed to 3: 7.
(Example 9)
223.3 g (2.94 mol) of propane-1,2-diol in Example 2; 254.6 g (2.44 mol) of neopentyl glycol; 239.9 g (2.44 mol) of maleic anhydride; Except that an unsaturated polyester having an acid value of 25 mg KOH / g, a viscosity of 2.2 Pa 占 퐏 and a number average molecular weight of 8,500 was further added in an amount of 0.025 g, to obtain 362.2 g (2.44 mol) of phthalic anhydride. .
(Example 10)
An ultraviolet curable coating composition was prepared in the same manner as in Example 2 except that 0.005 g of behenamide (Finawax B, Fine Organics) was further added.
(Example 11)
An ultraviolet curable coating composition was prepared in the same manner as in Example 2 except that 0.025 g of the unsaturated polyester of Example 9 and 0.005 g of behenamide of Example 10 were further added.
(Comparative Example)
10 g of urethane acrylate (PU-240) as an acrylic oligomer and 2 g of methyl methacrylate as an acrylic monomer were mixed, 0.36 g (3% by weight) of an α-hydroxy ketone type Irgacure 184 (Irgacure 184) At 400 rpm for 10 minutes to prepare an ultraviolet curable coating composition.
[Table 1]
As shown in Table 1, the hard coating composition according to the present invention exhibits excellent surface hardness as compared with the comparative example. In particular, Example 11 in which an unsaturated polyester and a slipping agent were further added showed better values in terms of better transmittance than the other Examples and Comparative Examples. However, in the case of Example 1, it was found that the condensation product using Vinyltrimethoxysilane did not maintain transparency when mixed with acrylic resin. This is because the vinyl group contained in the vinyltrimethoxysilane and the acrylate group of the acrylic resin have different chemical structures and the transparency is poor because of poor compatibility when mixed.
While the present invention has been particularly shown and described with reference to exemplary embodiments and comparative examples, it is to be understood that the invention is not limited to the disclosed exemplary embodiments and comparative examples, It is necessary to judge what is described in the detailed description of FIG.
Claims (8)
[Chemical Formula 1]
(Wherein R 1 is each independently hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) aryl;
R 2 each independently represents a group selected from the group consisting of (C 1 -C 20) carboxyl, sulfonic acid, epoxy, acryl, methacryl, halogen, A vinyl group, a naphthyl group, an oxetane group and a phenyl group;
and n is an integer of 5 to 100 or less.
The UV curable coating composition comprises 30 to 50% by weight of an organosiloxane, 40 to 60% by weight of an acrylic monomer, 5 to 10% by weight of an unsaturated polyester, 0.1 to 5% by weight of a linear saturated fatty acid amide having 10 to 25 carbon atoms, 5% by weight based on the total weight of the composition.
The acrylic monomer may be selected from the group consisting of methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, Acrylate, benzyl acrylate, methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate and benzyl acrylate. Curable coating composition.
The unsaturated polyester has a number average molecular weight of 1,000 to 10,000 and an acid value of 10 to 35 mg KOH / g.
The photoinitiator may be selected from benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylmethane- 2-methoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone,? -Hydroxy ketone, 4-phenoxydichloroacetone, 4 methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-hydroxy-2-methylpropan- Phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime, benzoin, benzyl, benzophenone, benzoylbenzoic acid, 3,3'-methyl-4-methoxybenzophenone, polyvinyl Benzophenone,? -Hydroxycyclohexylbenzophenone, benzylmethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2 , 4-dichlorothioxanthone, 2,4-diethylthio Oxacanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
Wherein the ultraviolet curable coating composition further comprises one or two or more additives selected from a colloid stabilizer, a wetting agent, an anti-scratch agent, an antifouling agent and an ultraviolet stabilizer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000007717A (en) | 1998-06-19 | 2000-01-11 | Takeda Chem Ind Ltd | Ultraviolet-curing resin composition |
| JP2013010744A (en) | 2011-05-30 | 2013-01-17 | Dow Corning Toray Co Ltd | Novel organopolysiloxane elastomer and use of the same |
| JP5664850B2 (en) * | 2010-10-04 | 2015-02-04 | セイコーエプソン株式会社 | UV curable ink composition for inkjet |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000007717A (en) | 1998-06-19 | 2000-01-11 | Takeda Chem Ind Ltd | Ultraviolet-curing resin composition |
| JP5664850B2 (en) * | 2010-10-04 | 2015-02-04 | セイコーエプソン株式会社 | UV curable ink composition for inkjet |
| JP2013010744A (en) | 2011-05-30 | 2013-01-17 | Dow Corning Toray Co Ltd | Novel organopolysiloxane elastomer and use of the same |
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