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WO2017217522A1 - Composition de résine durcissable par rayonnement actinique et matériau de revêtement la contenant - Google Patents

Composition de résine durcissable par rayonnement actinique et matériau de revêtement la contenant Download PDF

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Publication number
WO2017217522A1
WO2017217522A1 PCT/JP2017/022246 JP2017022246W WO2017217522A1 WO 2017217522 A1 WO2017217522 A1 WO 2017217522A1 JP 2017022246 W JP2017022246 W JP 2017022246W WO 2017217522 A1 WO2017217522 A1 WO 2017217522A1
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Prior art keywords
meth
acrylate
compound
curable resin
resin composition
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PCT/JP2017/022246
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English (en)
Japanese (ja)
Inventor
亮輔 谷口
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Mitsubishi Chemical Corp
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Nippon Synthetic Chemical Industry Co Ltd
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Priority to CN201780033168.4A priority Critical patent/CN109196009B/zh
Priority to KR1020187034599A priority patent/KR20190019924A/ko
Priority to JP2017533366A priority patent/JP6950527B2/ja
Publication of WO2017217522A1 publication Critical patent/WO2017217522A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to an active energy ray-curable resin composition and a coating agent. More specifically, when a cured coating film is used, the coating film has excellent hardness and scratch resistance, and further has a water vapor barrier property and an oxygen barrier property.
  • the present invention relates to an active energy ray-curable resin composition capable of obtaining a cured coating film excellent in a well-balanced gas barrier property and flexibility, and a coating agent using the same.
  • active energy ray-curable resin compositions are cured by irradiation with active energy rays such as radiation and ultraviolet rays for a very short time, so that coating agents and adhesives for various substrates, anchor coating agents, etc.
  • active energy rays such as radiation and ultraviolet rays
  • plastic films are widely used as optical member applications such as liquid crystal displays, and these plastic films have the drawback of being easily scratched on the surface, so that they are coated to impart hardness and scratch resistance. It is used by applying an agent, particularly a hard coat coating agent.
  • these hard coat coating agents improve the process suitability of the plastic film on which the cured coating film has been formed.
  • it is required to have high flexibility so that cracks and the like do not occur even when a plastic film having a cured coating film is bent.
  • an organic EL that has been developed in recent years, it is known that the display element is weak against moisture and deteriorates due to humidity in the environment. Therefore, in a plastic film used for a display device using an organic EL, a high water vapor barrier property is required for the hard coat layer so as not to cause a display defect and a decrease in visibility due to moisture intrusion. Yes.
  • Patent Document 1 discloses an active energy ray containing urethane (meth) acrylate, tripentaerythritol octa (meth) acrylate, and a polymerization initiator.
  • a curable resin composition has been disclosed, and it has been shown that when this resin composition is applied to a plastic film, a high hardness can be obtained and a cured coating film having excellent flexibility can be obtained.
  • Patent Document 2 discloses a urethane having an ethylenically unsaturated double bond obtained by reacting a polyolefin polyol compound, an ethylenically unsaturated compound having a hydroxyl group, and a compound having two or more isocyanate groups in one molecule.
  • a photocurable resin composition containing a compound, a photopolymerizable monomer, a photopolymerization initiator, and a urethane acrylate oligomer is disclosed, and has flexibility and low moisture permeability, and further has an adhesive property to a polyethylene terephthalate (PET) substrate. Shown to combine.
  • the cured coating film disclosed in Patent Document 1 has a flexibility evaluation of 6 to 10 using a mandrel tester (see Table 1). In the case of a flexible display application or when a film is bent, it is required that the evaluation of bendability by a mandrel testing machine is 5 or less. Therefore, the cured coating film disclosed in Patent Document 1 has bendability. Insufficient. Moreover, it does not have a water vapor barrier property.
  • Patent Document 2 Although it has water vapor barrier properties, the resin is soft, and when it is used as a cured coating film, it cannot satisfy hardness and scratch resistance, and is applicable to hard coat applications. It was difficult.
  • the inventor of the present invention contains a large amount of isocyanurate structure in one molecule in an active energy ray-curable resin composition containing a urethane (meth) acrylate compound.
  • a urethane (meth) acrylate compound By using a urethane (meth) acrylate compound, it is possible to obtain an active energy ray-curable resin composition having a good balance of hardness, scratch resistance, flexibility, and gas barrier properties when formed into a cured coating film. I found.
  • the gist of the present invention relates to an active energy ray-curable resin composition comprising a urethane (meth) acrylate compound (A) having three or more average isocyanurate structures per molecule. Moreover, this invention relates also to the coating agent formed using the said active energy ray curable resin composition.
  • the active energy ray-curable resin composition of the present invention contains a urethane (meth) acrylate compound (A) having three or more average isocyanurate structures per molecule.
  • a cured coating film having gas barrier properties such as water vapor barrier properties and oxygen barrier properties, and also excellent in flexibility can be obtained.
  • the urethane (meth) acrylate compound (A) is a reaction product urethane of a hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure other than the isocyanurate compound (a1) and the component (a1).
  • the compound is a (meth) acrylate compound (A1)
  • the cured coating film is more excellent in balance between gas barrier properties and flexibility.
  • the urethane (meth) acrylate compound (A) is an isocyanurate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure other than the component (a1), and a chain extender (a3).
  • the urethane (meth) acrylate compound (A2) is a reaction product, the balance between gas barrier properties and flexibility of the cured coating film is improved.
  • the cured coating film has better gas barrier properties.
  • the weight average molecular weight of the urethane (meth) acrylate compound (A) is 1,000 to 20,000, the balance between the flexibility and hardness of the cured coating film is further improved.
  • the reaction product is formed by reacting at a molar ratio of 2 to 1:10, the content of the urethane acrylate compound can be sufficiently obtained, so that the flexibility is further improved.
  • the cured coating film is further improved due to the balance of scratch resistance, flexibility and gas barrier properties.
  • the isocyanurate structure-containing concentration in the curing component contained in the active energy ray-curable resin composition is 1.0 mmol / g or more, the gas barrier property, the flexibility of the cured coating film, and the balance of hardness are further improved. Become.
  • the active energy ray-curable resin composition When used as a coating agent, a cured coating film having a good balance in hardness, scratch resistance, flexibility, and water vapor barrier properties can be obtained.
  • (meth) acryl means acryl or methacryl
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acryloyloxy means acryloyloxy or methacryloyloxy.
  • the active energy ray-curable resin composition of the present invention is characterized by containing a urethane (meth) acrylate compound (A) having three or more average isocyanurate structures per molecule.
  • the number of average isocyanurate structures per molecule is preferably 3.5 or more, particularly preferably 4.0 or more, more preferably 4.5 or more, and the upper limit is usually 100, preferably 50. More preferably, the number is 30. If the number of average isocyanurate structures is small, gas barrier properties and flexibility will be reduced.
  • the urethane (meth) acrylate compound (A) used in the present invention has three or more average isocyanurate structures per molecule, and in order for the urethane (meth) acrylate compound to contain an isocyanurate structure, In a urethane (meth) acrylate compound obtained by reacting an isocyanate compound and a hydroxyl group-containing (meth) acrylate compound, either or both of the isocyanate compound and the hydroxyl group-containing (meth) acrylate compound is isocyanate. What is necessary is just to make it react using what has a nurate structure. Especially, what made it react using what has an isocyanurate structure in both is preferable at the point which is excellent in the gas-barrier property and flexibility of a cured coating film.
  • an isocyanurate compound (a1) is used as the isocyanate compound, and a hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure as the hydroxyl group-containing (meth) acrylate compound (however, the isocyanurate)
  • a urethane (meth) acrylate compound (A1) obtained by reacting (a1) and (a2) using a system compound (a1) is a balance between gas barrier properties and flexibility of a cured coating film. It is preferable at the point which is excellent in.
  • the urethane (meth) acrylate compound (A) is an isocyanurate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure, and a chain extender (a3). It is also preferred that the reaction product is a urethane (meth) acrylate compound (A2).
  • an isocyanurate compound (a1) is used as the isocyanate compound, and a hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure as the hydroxyl group-containing (meth) acrylate compound (however, the isocyanurate)
  • a urethane (meth) acrylate compound (A2) obtained by reacting (a1) to (a3) with a chain extender (a3). This is preferable because the cured coating film has an excellent balance between gas barrier properties and flexibility.
  • the isocyanurate compound (a1) used as the isocyanate compound is a polyvalent isocyanate having an isocyanurate structure.
  • Aromatic polyisocyanates such as aromatic diisocyanates (eg, tolylene diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate); Aliphatic polyisocyanates such as aliphatic diisocyanates (eg, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate) and aliphatic triisocyanates (eg, lysine triisocyanate); Cycloaliphatic polyisocyanates such as cycloalipha
  • isocyanurate body although a trimer and a higher multimer are mention
  • isocyanurate of diisocyanate is preferable in terms of the excellent balance between scratch resistance and flexibility of the cured coating film, and isocyanurate of aliphatic diisocyanate is particularly preferable in terms of excellent water vapor barrier properties.
  • the isocyanurate of hexamethylene diisocyanate is more preferable in terms of excellent versatility.
  • Aromatic polyisocyanates such as aromatic diisocyanates (for example, tolylene diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, etc.); Aliphatic polyisocyanates such as aliphatic diisocyanates (eg, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate) and aliphatic
  • hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure is used as the hydroxyl group-containing (meth) acrylate compound.
  • hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure for example, Isocyanuric acid ethylene oxide modified mono (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid propylene oxide modified mono (meth) acrylate, isocyanuric acid propylene oxide modified di (meth) acrylate, etc.
  • Isocyanuric acid polyalkylene oxides such as oxide-modified mono (meth) acrylate, isocyanuric acid triethylene oxide-modified di (meth) acrylate, isocyanuric acid tripropylene oxide-modified mono (meth) acrylate, isocyanuric acid tripropylene oxide-modified di (meth) acrylate
  • Modified mono- or di (meth) acrylate; 1 type can be used individually or in combination of 2 or more types.
  • isocyanuric acid alkylene oxide modified mono (meth) acrylate isocyanuric acid alkylene oxide modified di (meth) acrylate, isocyanuric acid propylene oxide modified mono (meth) acrylate, isocyanuric acid propylene oxide modified di ( (Meth) acrylate is preferable, and isocyanuric acid ethylene oxide-modified mono (meth) acrylate and isocyanuric acid ethylene oxide-modified di (meth) acrylate are particularly preferable from the viewpoint of excellent balance of scratch resistance, flexibility and gas barrier properties of the cured coating film.
  • the number average molecular weight of the hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure is preferably 200 to 2,000 from the viewpoint of excellent gas barrier properties of the cured coating film, particularly preferably 300 to 1. , 500.
  • the hydroxyl group-containing (meth) acrylate compound may not have an isocyanurate structure.
  • the containing (meth) acrylate compound for example, Hydroxyalkyl (meta) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc.
  • the chain extender (a3) has a function of increasing the molecular weight of the urethane (meth) acrylate compound.
  • a polyol compound is preferable, and an aliphatic polyol and a ring structure-containing polyol are preferable from the viewpoint of excellent gas barrier properties.
  • a cured film having a particularly high glass transition temperature (Tg) is obtained, and the gas barrier properties are excellent.
  • neopentyl glycol is a 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, ethylene oxide adduct of isocyanuric acid, propylene oxide adduct of isocyanuric acid among the ring structure-containing polyols. preferable.
  • These chain extenders (a3) can be used alone or in combination of two or more.
  • the number average molecular weight of the chain extender (a3) is preferably 30 to 500, more preferably 50 to 400, and particularly preferably 70 to 300. If it is too large, the hardness and gas barrier properties tend to decrease, and if it is too small, the flexibility tends to decrease.
  • the urethane (meth) acrylate compound (A1) used in the present invention has a functional group molar ratio between the isocyanate group of the isocyanurate compound (a1) and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2). It can be obtained by reacting the isocyanurate compound (a1) with the hydroxyl group-containing (meth) acrylate compound (a2) using a reaction catalyst such as dibutyltin dilaurate or a polymerization inhibitor as necessary. it can.
  • reaction catalyst for the purpose of promoting the reaction.
  • dibutyltin Organometallic compounds such as dilaurate, trimethyltin hydroxide and tetra-n-butyltin, zinc octenoate, tin octenoate, tin octylate, cobalt naphthenate, stannous chloride, stannic chloride and other metal salts, triethylamine , Benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl-1,3-butane Amine-based catalysts such as diamine and N-ethylmorpholine
  • a polymerization inhibitor from the viewpoint of reaction stability during production.
  • an organic solvent having no functional group that reacts with an isocyanate group such as ethyl acetate, butyl acetate, etc.
  • Organic solvents such as esters, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene can be used.
  • an ethylenically unsaturated compound (B) can be made into a dilution monomer, and can also be made to react in this presence.
  • the urethane (meth) acrylate compound (A2) used in the present invention also includes the isocyanate group of the isocyanurate compound (a1), the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2), and a chain extender (a3).
  • the reaction group such as dibutyltin dilaurate or a polymerization inhibitor, if necessary, isocyanurate compound (a1), hydroxyl group-containing (meth) acrylate compound ( It can be obtained by reacting a2) and a chain extender (a3).
  • reaction conditions etc. it can carry out according to the case of a urethane (meth) acrylate type compound (A1).
  • the urethane (meth) acrylate compound (A) used in the present invention preferably has an isocyanurate structure-containing concentration of 1.3 mmol / g or more, particularly preferably 1.5 to 3.0 mmol / g, more preferably Is 1.8 to 2.5 mmol / g.
  • the isocyanurate structure-containing concentration of the urethane (meth) acrylate compound (A) is too high, the cured coating film tends to be soft and the scratch resistance tends to decrease, and when it is too low, the gas barrier property tends to decrease. Moreover, since a cured coating film becomes hard, there exists a tendency for a flexibility to fall.
  • the isocyanurate structure-containing concentration of the urethane (meth) acrylate compound (A) is determined based on the constituent materials of the urethane (meth) acrylate compound (A) (isocyanate compound, hydroxyl group-containing (meth) acrylate compound, (if necessary The chain extender)) is calculated from the following formula 1.
  • Isocyanurate structure-containing concentration (mmol / g) 1000 ⁇ ⁇ (N ⁇ W / M)
  • N Number of average isocyanurate structures contained in each constituent raw material
  • W Weight ratio of each constituent raw material in urethane (meth) acrylate compound (A)
  • M Number average molecular weight of each constituent raw material
  • N i (A i ⁇ M i / 4202) ⁇ 2
  • a i Weight ratio of isocyanate group contained in isocyanate compound
  • M i Number average molecular weight of isocyanate compound
  • the number average molecular weight is a number average molecular weight in terms of standard polystyrene molecular weight.
  • ACQUITY APC XT is used for high performance liquid chromatography (“Waters Corporation,“ ACQUITY APC system ”). It can be measured by using four lines of 200 ⁇ 1 and ACQUITY APC XT 45 ⁇ 2.
  • the isocyanurate structure-containing concentration of the urethane (meth) acrylate compound (A) is adjusted, for example, by changing the charging ratio between the reaction raw material containing the isocyanurate structure and the reaction raw material not containing the isocyanurate structure. Can do.
  • the urethane (meth) acrylate compound (A) used in the present invention preferably has a weight average molecular weight of 1,000 to 20,000, particularly preferably 1,200 to 18,000, and more preferably 1, 500 to 15,000, particularly preferably 2,000 to 10,000. If the weight average molecular weight is too large, the viscosity tends to be high and handling tends to be difficult. If it is too small, the balance between the flexibility and hardness of the cured coating film tends to be lowered.
  • said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, for example, a column: ACQUITY APC XT 450x1 in a high performance liquid chromatography (the product made by Waters, "ACQUITY APC system"), ACQUITY APC XT 200 ⁇ 1 and ACQUITY APC XT 45 ⁇ 2 in series can be used for measurement.
  • the urethane (meth) acrylate compound (A) can be used alone or in combination of two or more.
  • the active energy ray-curable resin composition of the present invention can further contain an ethylenically unsaturated compound (B).
  • the ethylenically unsaturated compound (B) include an ethylenically unsaturated group-containing monomer having one ethylenically unsaturated group (monofunctional monomer) and an ethylenically unsaturated group-containing monomer having two or more ethylenically unsaturated groups. (Polyfunctional monomer).
  • the monofunctional monomer examples include styrene monomers such as styrene, vinyl toluene, chlorostyrene, ⁇ -methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxy Propyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (Meth) acrylate, lauryl (meth) acrylate, cyclo
  • Examples of the polyfunctional monomer include a bifunctional monomer and a trifunctional monomer.
  • Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth).
  • Acrylate polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, cyclohexane dimethano Rudi (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Glycerin di (meth) acrylate, pentaerythritol di (meth
  • trifunctional or higher functional monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, capro Kuton modified pentaerythrito
  • a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination.
  • examples of such a Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, Acrylic acid tetramer, methacrylic acid tetramer, etc. are mentioned.
  • the 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl.
  • Examples thereof include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, other oligoester acrylates can be mentioned.
  • trimethylolpropane tri (meth) acrylate trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth)
  • a polyfunctional ethylenically unsaturated group-containing monomer such as acrylate.
  • 2-hydroxyethyl (meth) acrylate 4-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, carbitol (meth) acrylate, (meth) acryloyl morpholine. It is preferable to contain a monofunctional ethylenically unsaturated group-containing monomer such as phosphorus.
  • isocyanuric acid ethylene oxide modified triacrylate caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meta) ) Acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide High molecular weights such as modified pentaerythritol tetra (meth) acrylate Preferably contains an ethylenically unsaturated group-containing monomer.
  • an ethylenically unsaturated group-containing monomer (B1) having an isocyanurate structure it is preferable to contain an ethylenically unsaturated group-containing monomer (B1) having an isocyanurate structure. Moreover, it is preferable to contain the ethylenically unsaturated group-containing monomer (B1) having an isocyanurate structure in terms of excellent balance between scratch resistance and flexibility of the cured coating film and gas barrier properties, and the hardness of the cured coating film, From the point of excellent balance in all of scratch resistance, flexibility and gas barrier properties, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, etc.
  • ethylenically unsaturated group-containing monomer having a nurate structure It is particularly preferable to contain an ethylenically unsaturated group-containing monomer having a nurate structure.
  • Such ethylenically unsaturated compounds (B) may be used alone or in combination of two or more.
  • the ethylenically unsaturated compound (B) containing 50% by weight or more of the ethylenically unsaturated group-containing monomer (B1) having an isocyanurate structure balances the gas barrier property and flexibility of the cured coating film.
  • it is preferably 60% by weight or more, particularly 70% by weight or more.
  • the upper limit is usually 100% by weight.
  • the content of the ethylenically unsaturated compound (B) is preferably 10 to 900 parts by weight, particularly preferably 25 to 400 parts by weight, based on 100 parts by weight of the urethane (meth) acrylate compound (A). More preferably, it is 40 to 250 parts by weight.
  • the content of the ethylenically unsaturated compound (B) is too large, the balance between scratch resistance and flexibility of the resulting cured coating film tends to be impaired, and when it is too small, the hardness of the cured coating film tends to decrease. There is.
  • the ethylenically unsaturated compound (B) may be separately added to the active energy ray-curable resin composition of the present invention, or a raw material for producing a urethane (meth) acrylate compound (A) or the like. Alternatively, a part of the product may remain in the system during production.
  • the active energy ray-curable resin composition of the present invention preferably further contains a photopolymerization initiator (C) in order to efficiently perform curing with active energy rays.
  • C photopolymerization initiator
  • the photopolymerization initiator (C) is not particularly limited as long as it generates radicals by the action of light. Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl- 1- [4- (1-methylvinyl) phenyl] propanone oligomer, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2- Hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -fur Sulfon
  • Benzophenones 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4- Thioxanthones such as dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Acyl phosphine oxides such as phosphine oxide, 1,2-octanediene-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [
  • auxiliary agents for these photopolymerization initiators (C) include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethyl.
  • Benzoic acid ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone 2,4-diisopropylthioxanthone can also be used in combination.
  • These auxiliaries can be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (C) is 100 parts by weight of the urethane (meth) acrylate compound (A) (in the case where the ethylenically unsaturated compound (B) is contained, the total with (B)).
  • the amount is preferably 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, and further preferably 2 to 5 parts by weight. If the content is too small, the curing rate tends to decrease or the adhesive strength tends to decrease. If the content is too large, the curability is not improved and yellowing tends to occur under high temperature conditions.
  • the active energy ray-curable resin composition of the present invention can contain a polythiol compound from the viewpoint of suppressing unreacted components and improving adhesion.
  • the polythiol compound is not particularly limited, but a compound having 2 to 6 mercapto groups in the molecule is preferable.
  • aliphatic polythiols such as alkanedithiol having about 2 to 20 carbon atoms, aromatics such as xylylenedithiol, etc.
  • Polythiols polythiols obtained by replacing halogen atoms of halohydrin adducts of alcohols with mercapto groups, polythiols consisting of hydrogen sulfide reaction products of polyepoxide compounds, polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule And polythiols composed of esterified products with thioglycolic acid, ⁇ -mercaptopropionic acid, or ⁇ -mercaptobutanoic acid, and the like. These can be used alone or in combination of two or more. .
  • the content of the polythiol compound is 0.01 with respect to 100 parts by weight of the urethane (meth) acrylate compound (A) (the total of (A) and (B) when the ethylenically unsaturated compound (B) is contained).
  • the amount is preferably ⁇ 10 parts by weight, particularly preferably 0.1 to 5 parts by weight.
  • the active energy ray-curable resin composition of the present invention includes a urethane (meth) acrylate compound (A), an ethylenically unsaturated compound (B) contained as necessary, and a photopolymerization initiator (C). Furthermore, if necessary, urethane (meth) acrylate compounds other than urethane (meth) acrylate compounds (A), other crosslinkable group-containing compounds (D), acrylic resins, surface conditioners, leveling agents, polymerization Inhibitors can be added, and oils, antioxidants, flame retardants, antistatic agents, fillers, stabilizers, reinforcing agents, matting agents, abrasives, organic fine particles, inorganic particles, etc. It is also possible to do.
  • Examples of the other crosslinkable group-containing compound (D) include epoxy compounds, oxetane compounds, carboxylic acid compounds, aziridine compounds, polyisocyanate compounds, polyol compounds, and polyamine compounds.
  • the content when the other crosslinkable group-containing compound (D) is contained is 0.1 to 20 parts by weight with respect to 100 parts by weight of the curing component contained in the active energy ray-curable resin composition. It is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight.
  • the active energy ray-curable resin composition of the present invention preferably uses an organic solvent for dilution in order to adjust the viscosity during coating, if necessary.
  • organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene Aromatic glycols such as propylene glycol monomethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol.
  • organic solvents may be used alone or in combination of two or more.
  • two or more types are used in combination, it is preferable from the viewpoint of the coating film appearance that two or more types are selected and combined from glycol ethers, ketones, acetate esters, and alcohols.
  • the active energy ray-curable resin composition of the present invention requires that the isocyanurate structure-containing concentration in the curing component contained in the active energy ray-curable resin composition is usually 1.0 mmol / g or more, preferably Is 1.4 to 3.0 mmol / g, more preferably 1.6 to 2.5 mmol / g, and particularly preferably 1.8 to 2.2 mmol / g. If the isocyanurate structure-containing concentration is too high, the cured coating film becomes soft and the scratch resistance is lowered, and if it is too low, the water vapor barrier property is lowered, and the cured coating film becomes hard and the flexibility is also lowered.
  • the curing component includes a urethane (meth) acrylate compound (A), if necessary, the urethane (meth) acrylate compound other than the ethylenically unsaturated compound (B) and (A), and other crosslinkable properties.
  • a urethane (meth) acrylate compound (A) if necessary, the urethane (meth) acrylate compound other than the ethylenically unsaturated compound (B) and (A), and other crosslinkable properties.
  • group-containing compound (D) is contained, these are included.
  • the isocyanurate structure-containing concentration in the curing component contained in the active energy ray-curable resin composition is a urethane (meth) acrylate compound (A), an ethylenically unsaturated compound (B), and other crosslinkable group content. Based on each component of the compound (D), it is calculated by the following formula 3.
  • N i (A i ⁇ M i / 4202) ⁇ 2
  • a i Weight ratio of isocyanate group contained in isocyanate compound
  • M i Number average molecular weight of isocyanate compound
  • the urethane (meth) acrylate compound (A) is preferably at least 25% by weight, particularly preferably at least 30% by weight, more preferably at least 35% by weight, particularly preferably. Contains 40% by weight or more.
  • the upper limit is usually 100% by weight from the viewpoint of flexibility.
  • the viscosity (60 ° C.) of the active energy ray-curable resin composition of the present invention is preferably from 100 to 200,000 mPa ⁇ s, particularly preferably from 500 to 100,000 mPa ⁇ s from the viewpoint of coating property and the like. More preferably, it is 1,000 to 50,000 mPa ⁇ s. If the viscosity is too low, it tends to be difficult to control the film thickness at the time of coating, and if it is too high, handling tends to be difficult or the coating property tends to be lowered.
  • the viscosity is a viscosity measured using an E-type viscometer.
  • the active energy ray-curable resin composition of the present invention is effectively used as a curable resin composition for coating film formation, such as a top coat agent and an anchor coat agent for various substrates.
  • the active energy ray-curable resin composition of the present invention is useful for applications in which a cured coating film requires flexibility and gas barrier properties in addition to hardness and scratch resistance. It is useful as a surface coating agent for a protective member for a display member or touch panel, a coating agent for punching, or an adhesive between optical display members.
  • the active energy ray-curable resin composition of the present invention is irradiated with active energy rays after being applied to a base material (after further drying if a composition diluted with an organic solvent is applied). Can be cured.
  • Examples of the base material to which the active energy ray-curable resin composition of the present invention is applied include polyolefin resin, polyester resin, polycarbonate resin, acrylic resin acrylonitrile butadiene styrene copolymer (ABS), and polystyrene resin.
  • Metals aluminum, copper, iron, etc.
  • plastic base materials such as resins and their molded products (films, sheets, cups, etc.), composite base materials thereof, or composite base materials of the above-mentioned materials mixed with glass fibers and inorganic substances SUS, zinc, magnesium, alloys thereof, and the like, including a metal film such as a metal vapor deposition film), and a base material provided with a primer layer on a base material such as glass.
  • Examples of the coating method include wet coating methods such as spray, shower, dipping, roll, spin, curtain, flow, slit, die, gravure, comma, dispenser, screen printing, inkjet printing, etc. It can be applied to a substrate under normal temperature conditions.
  • rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron beams, proton rays, neutron rays, etc.
  • Curing by ultraviolet irradiation is advantageous because of its availability and price.
  • electron beam irradiation it can harden
  • UV irradiation When curing by ultraviolet irradiation, use a high-pressure mercury lamp, ultra-high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED, etc. that emits light in the wavelength range of 150 to 450 nm.
  • ultraviolet rays of 30 to 3000 mJ / cm 2 (preferably 100 to 1500 mJ / cm 2 ) can be irradiated. After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.
  • the film thickness of the cured film is usually 1 to 1000 ⁇ m, preferably 2 to 500 ⁇ m, and particularly preferably 5 to 200 ⁇ m.
  • the water vapor permeability of the cured coating film is preferably 100 g / m 2 ⁇ day or less, particularly 90 g / m 2 ⁇ day or less, more preferably 80 g / m 2 ⁇ day or less. .
  • the lower limit of the water vapor permeability is 0 g / m 2 ⁇ day.
  • the water vapor transmission rate is a value measured in a 40 ° C., 90% RH atmosphere by using a cup method according to JIS Z 0208 using a cured coating single layer having a film thickness of about 50 ⁇ m.
  • the cured film has an oxygen permeability of preferably 20 cc / m 2 ⁇ day ⁇ atm or less, particularly 15 cc / m 2 ⁇ day ⁇ atm or less, more preferably 10 cc / m 2 ⁇ day ⁇ atm.
  • the following is preferable.
  • the lower limit of oxygen permeability is 0 cc / m 2 ⁇ day ⁇ atm.
  • the oxygen permeability is measured under the conditions of 23 ° C. and 80% RH using a PET film provided with a coating layer having a film thickness of about 70 ⁇ m and using an oxygen permeability tester (manufactured by MOCON, “Oxtran 100A”). Went. Thereafter, the oxygen permeability (cc / m 2 ⁇ day ⁇ atm) of a cured coating single layer having a thickness of 100 ⁇ m was calculated.
  • reaction was terminated when it became 3% or less, and urethane (meth) acrylate compound (A′-2) having no isocyanurate structure (A′-2) (weight average molecular weight (Mw): 2,200), 44.0 g, 8.6 g of unreacted portion of dipentaerythritol pentaacrylate (B-3); A mixture with 47.4 g of dipentaerythritol hexaacrylate (B-2) was obtained.
  • Example 1 A mixture of 45 parts of the urethane (meth) acrylate compound (A1-1) obtained in Production Example 1 above and 55 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1), 1 as the photopolymerization initiator (C) 4 parts of hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure 184”) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray-curable resin composition.
  • the isocyanurate structure-containing concentration in the cured component contained in the obtained active energy ray-curable resin composition was 2.02 mmol / g.
  • Example 2 A mixture of 44 parts of the urethane (meth) acrylate compound (A1-2) obtained in Production Example 2 above and 56 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1), 1 as the photopolymerization initiator (C) 4 parts of hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure 184”) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray-curable resin composition.
  • the isocyanurate structure-containing concentration in the cured component contained in the obtained active energy ray-curable resin composition was 1.97 mmol / g.
  • Example 3 A mixture of 44 parts of the urethane (meth) acrylate compound (A1-3) obtained in Production Example 3 above and 56 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1), 1 as the photopolymerization initiator (C) 4 parts of hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure 184”) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray-curable resin composition.
  • the isocyanurate structure-containing concentration in the cured component contained in the obtained active energy ray-curable resin composition was 1.94 mmol / g.
  • Example 4 A mixture of 73 parts of the urethane (meth) acrylate compound (A1-4) obtained in Production Example 4 and 27 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1), 1 as the photopolymerization initiator (C) 4 parts of hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure 184”) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray-curable resin composition.
  • the isocyanurate structure-containing concentration in the cured component contained in the obtained active energy ray-curable resin composition was 2.02 mmol / g.
  • Example 5 A mixture of 51 parts of the urethane (meth) acrylate compound (A2-1) obtained in Production Example 5 above and 49 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1), 1 as the photopolymerization initiator (C) 4 parts of hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure 184”) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray-curable resin composition.
  • the isocyanurate structure-containing concentration in the curing component contained in the obtained active energy ray-curable resin composition was 1.91 mmol / g.
  • An active energy ray-curable resin composition was obtained.
  • the isocyanurate structure-containing concentration in the cured component contained in the obtained active energy ray-curable resin composition was 0 mmol / g.
  • ⁇ Comparative example 4 100 parts of the urethane (meth) acrylate compound (A′-3) obtained in Comparative Production Example 3 above, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure” as a photopolymerization initiator (C) 184 ”) and 150 parts of toluene as a diluent solvent were uniformly mixed to obtain an active energy ray-curable resin composition.
  • the isocyanurate structure-containing concentration in the cured component contained in the obtained active energy ray-curable resin composition was 0 mmol / g.
  • the active energy ray-curable resin composition obtained in Comparative Example 4 above was cured using a bar coater on a 125 ⁇ m-thick PET film provided with an easy-adhesion layer.
  • the film was coated so as to have a film thickness, and dried at 90 ° C. for 3 minutes.
  • two passes of ultraviolet irradiation (accumulated irradiation amount 800 mJ / cm 2 ) were carried out at a conveyor speed of 3.4 m / min from a height of 18 cm to form a cured coating film. .
  • the film thickness after curing of the active energy ray-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 is about 50 ⁇ m.
  • the laminate was laminated with a release PET film. Then cut into a 7cm diameter circle, and using a high pressure mercury lamp 80W and 1 lamp, 2 passes of UV irradiation (cumulative irradiation dose 500mJ / cm 2 ) from a height of 18cm at a conveyor speed of 5.1m / min. A sheet with a cured coating film was formed.
  • the untreated PET film and the peeled PET film were peeled off from the above sheet, and the cured coating film single layer was taken out and used as a sample for measuring water vapor permeability. Further, the active energy ray-curable resin composition obtained in Comparative Example 4 was applied on an untreated PET film using an applicator so that the film thickness after curing was about 50 ⁇ m, and 90 ° C. For 20 minutes, and then laminated with a release PET film. Then cut into a circle with a diameter of 7 cm, and using a high pressure mercury lamp 80 W and one lamp, two passes of UV irradiation (accumulated dose 800 mJ / cm 2 ) from a height of 18 cm at a conveyor speed of 3.4 m / min.
  • a sheet with a cured coating film was formed.
  • the untreated PET film and the peeled PET film were peeled off from the above sheet, and the cured coating film single layer was taken out and used as a sample for measuring water vapor permeability.
  • the water vapor transmission rate was measured by a cup method according to JIS Z 0208 and evaluated in an atmosphere of 40 ° C. and 90% RH.
  • the evaluation criteria are as follows. (Evaluation) ⁇ ... Water vapor permeability is 50 g / m 2 ⁇ day or less ⁇ ... Water vapor permeability is greater than 50 g / m 2 ⁇ day
  • the film thickness after curing of the active energy ray-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 is about 70 ⁇ m.
  • the film thickness after curing of the active energy ray-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 is about 70 ⁇ m.
  • the active energy ray-curable resin composition obtained in Comparative Example 4 was applied onto an untreated PET film using an applicator so that the film thickness after curing was approximately 70 ⁇ m, and 90 ° C.
  • the evaluation criteria are as follows. (Evaluation) ⁇ ⁇ ⁇ ⁇ Oxygen permeability is less than 10cc / m 2 ⁇ day ⁇ atm ⁇ ⁇ ⁇ ⁇ Oxygen permeability is greater than 10cc / m 2
  • the active energy ray-curable resin compositions of Examples 1 to 5 can provide cured coatings having a good balance in hardness, scratch resistance, flexibility, water vapor barrier property and oxygen barrier property. . Therefore, even when the active energy ray-curable resin compositions of Examples 1 to 5 were used as a coating agent, they were excellent in balance in hardness, scratch resistance, flexibility, water vapor barrier property and oxygen barrier property.
  • Comparative Example 1 in which the number of isocyanurate structures per molecule in the composition is lower than that defined in the present invention, the cured film has insufficient flexibility. Further, in Comparative Example 2 containing a urethane (meth) acrylate compound having no isocyanurate structure and not containing a urethane (meth) acrylate compound having an isocyanurate structure, water vapor permeability and oxygen permeability are high, The gas barrier property was inferior and the flexibility was not obtained. In Comparative Example 3 which did not contain a urethane (meth) acrylate compound and used only an ethylenically unsaturated monomer having an isocyanurate structure, the flexibility of the cured coating film was insufficient.
  • Comparative Example 4 that was not performed was inferior in hardness and scratch resistance. That is, in the active energy ray-curable resin composition of the comparative example that does not satisfy the constituent requirements of the present invention, a cured coating film that satisfies all of the hardness, scratch resistance, flexibility, and gas barrier properties in a well-balanced manner cannot be obtained. there were.
  • the active energy ray-curable resin composition of the present invention is useful as various film forming materials.
  • it is useful as various coating agents such as optical display members, touch panel protective film coatings, and undercoats.
  • It is also useful as an adhesive layer between optical display members and a sealing material for organic EL display elements.
  • a gas barrier film or sheet can also be formed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de résine durcissable par rayonnement actinique qui comprend un composé (méth)acrylate d'uréthane (A) ayant au moins trois structures isocyanurate en moyenne par molécule. La composition de résine durcissable par rayonnement actinique peut former un film de revêtement durci qui présente un excellent équilibre entre non seulement la dureté et la résistance aux rayures mais également des propriétés de barrière aux gaz, par exemple, des propriétés de barrière à la vapeur d'eau et des propriétés de barrière à l'oxygène, et des propriétés de flexion.
PCT/JP2017/022246 2016-06-17 2017-06-16 Composition de résine durcissable par rayonnement actinique et matériau de revêtement la contenant Ceased WO2017217522A1 (fr)

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KR1020187034599A KR20190019924A (ko) 2016-06-17 2017-06-16 활성 에너지선 경화성 수지 조성물 및 이를 사용하여 이루어진 코팅제
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