WO2015001949A1 - 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体 - Google Patents
活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体 Download PDFInfo
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- WO2015001949A1 WO2015001949A1 PCT/JP2014/065979 JP2014065979W WO2015001949A1 WO 2015001949 A1 WO2015001949 A1 WO 2015001949A1 JP 2014065979 W JP2014065979 W JP 2014065979W WO 2015001949 A1 WO2015001949 A1 WO 2015001949A1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- 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
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- 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
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- C09D173/00—Coating compositions based on macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C09D159/00 - C09D171/00; Coating compositions based on derivatives of such polymers
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/105—Esters of polyhydric alcohols or polyhydric phenols of pentaalcohols
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
Definitions
- the present invention is an active energy ray-curable resin composition that is excellent in storage stability and further has a high level of applicability to various substrates, adhesion, and appearance and heat resistance of a cured coating film.
- the present invention relates to an active energy ray-curable resin composition suitably used as an undercoating coating agent for performing metal vapor deposition on a molded body formed by combining a plurality of resin types.
- Base materials used for such applications include BMC (bulk molding compound), PPS (polyphenylene sulfide), ALD (aluminum die cast), PBT (polybutylene terephthalate) / PET (polyethylene terephthalate) alloy resin, PC (polycarbonate). ), ABS (Acrylonitrile-Butadiene-Styrene Copolymer), PC (polycarbonate) reinforced with fillers such as glass fiber, etc., and has excellent heat resistance and impact resistance.
- plastic base materials are often used from the viewpoint of weight reduction.
- the reflector of the headlamp lens of automobile parts is a combination of a plurality of types of base materials.
- a base material with excellent heat resistance is used for the part close to the lamp light source, and a base material with excellent workability is used for the part far from the lamp light source because the base material shape is complicated.
- a coating agent depending on the type of substrate.
- automotive headlamp lens reflectors but parts with a metal-like surface appearance to give high appearance to automotive parts such as mobile phones, grills, emblems, cosmetic containers, home appliances, etc.
- a metal such as tin or aluminum on the surface thereof.
- an active energy ray-curable undercoating coating agent that can be applied to various plastic substrates in order to smooth the surface and improve the adhesion between the plastic substrate and the metal vapor-deposited film. Is required.
- the problem to be solved by the present invention is an active energy ray that is excellent in storage stability and further has a high level of coating properties and adhesion to various substrates, and appearance and heat resistance of a cured coating film.
- the object is to provide a curable resin composition, an active energy ray-curable undercoating coating agent for metal vapor deposition using the same, and a molded article having an undercoat layer for metal vapor deposition that has excellent adhesion to various substrates. .
- the inventors of the present invention have obtained an oil-modified alkyd resin having a high molecular weight and a wide molecular weight distribution obtained by using two or more kinds of specific oils and fats, and a (meth) acryloyl group. It has been found that the above-mentioned problems can be solved by using an active energy ray-curable resin composition that contains a compound having an essential component as an essential component, and the present invention has been completed.
- the present invention is an active energy ray-curable resin composition containing an oil-modified alkyd resin (A) and a compound (B) having a (meth) acryloyl group, the oil-modified alkyd resin (A).
- the oil length is 30 to 60
- the mass average molecular weight is 200,000 to 1,000,000
- the molecular weight distribution (Mw / Mn) is 50 or more, which is obtained by using two or more fats and oils (a1) having an iodine value of 100 or more.
- An active energy ray-curable resin composition characterized by being an oil-modified alkyd resin, an active energy ray-curable undercoat coating agent for metal deposition using the same, and a molding having an undercoat layer comprising the undercoat coating agent Provide the body.
- an active energy ray-curable resin composition that is excellent in coating suitability, adhesion, and storage stability to various plastic substrates.
- the cured coating film obtained from the composition has good appearance and heat resistance, so it is excellent in applicability to a molded body having a complicated shape and a molded body formed by combining multiple types of substrates. It can be suitably used as a coating agent for undercoating metal vapor deposition.
- the oil length is 30 to 60 and the mass average molecular weight is 200,000 to 1,000,000 obtained by using two or more oils and fats (a1) having an iodine value of 100 or more in combination.
- the oil-modified alkyd resin (A) having a molecular weight distribution (Mw / Mn) of 50 or more and the compound (B) having a (meth) acryloyl group are contained as essential components.
- the oil-modified alkyd resin is usually a resin obtained by condensation of a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol using a drying oil, semi-drying oil, non-drying oil or a fatty acid thereof as a modifier. It is.
- the oil-modified alkyd resin is obtained by using two or more oils and fats (a1) having an iodine value of 100 or more, and has an oil length of 30 to 60 and a mass average molecular weight of 200,000.
- Examples of the oil (a1) having an iodine value of 100 or more include kiri oil, linseed oil, dehydrated castor oil, soybean oil, safflower oil, tall oil and the like. From the viewpoint of adhesion to the substrate, linseed oil, soybean oil, safflower oil, and tall oil are preferably used.
- the molecular weight distribution range of the alkyd resin (A) to be obtained is widened, and it is easy to express adhesion to the substrate and anti-sagging, and easily obtain a composition excellent in coating suitability. Can do.
- it is possible to maintain the uniformity of the resulting oil-modified alkyd resin by using two or more types of oils and fats in combination from the raw material stage, rather than using a mixture of a plurality of types of the alkyd resins after being synthesized as an alkyd resin.
- the combination and mixing ratio of two or more kinds of fats and oils (a1) are not particularly limited, and can be appropriately set according to the intended oil length of the obtained oil-modified alkyd resin (A).
- the iodine value of the fat (a1) is 100 or more.
- the oil-modified alkyd resin (A) used in the present invention is a product having a high molecular weight and a wide molecular weight distribution as described above. From the viewpoint that such a resin can be easily obtained, an intramolecular polyhydric alcohol is used. It is preferable to use a branched alkane-type polyol (a2) having 3 or more hydroxyl groups and a polybasic acid (a3) having a cyclic unsaturated group in the molecule.
- Examples of the branched alkane-type polyol (a2) include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol; the aliphatic polyols, ethylene oxide, propylene oxide, tetrahydrofuran, and ethyl.
- Modified polyether polyols obtained by ring-opening polymerization with various cyclic ether bond-containing compounds such as glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, the aliphatic polyols, and various lactones such as ⁇ -caprolactone; Lactone polyester polyols obtained by the polycondensation reaction, and the like, from the viewpoint of improving the cross-linking density and obtaining a coating film having good heat resistance and toughness, trimethylolethane, Trimethylolpropane, pentaerythritol, it is preferable to use glycerin.
- polybasic acid (a3) examples include (anhydrous) aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and orthophthalic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid.
- aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and orthophthalic acid
- alicyclic dicarboxylic acids such as hexahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid.
- An acid etc. are mentioned, You may use individually or in combination of 2 or more types.
- various monocarboxylic acids can be used in combination for the preparation of the molecular weight of the alkyd resin (A) to be obtained.
- a monocarboxylic acid having a cyclic structure such as benzoic acid.
- the method for producing the oil-modified alkyd resin (A) is not particularly limited, and for example, after reacting fats and oils with alcohols in the presence of a catalyst (esterification reaction or transesterification reaction), further Examples include a method in which an acid is added to cause a reaction (esterification reaction) and a method in which an oil and fat used as a raw material, an alcohol, and an acid are charged and reacted together. The progress of the reaction can be monitored by measuring the amount of water distilled by the dehydration reaction, the acid value or the hydroxyl value.
- the oil length of the oil-modified alkyd resin (A) obtained above is essentially in the range of 30-60, and more preferably in the range of 40-50.
- the oil length is the percentage of the fat and oil component mass ratio to the total mass of unsaturated fatty acids or unsaturated fatty acid esters in the oils and carboxylic acids and fats and oils as raw materials.
- the mass average molecular weight (Mw) of the oil-modified alkyd resin (A) used in the present invention must be in the range of 200,000 to 1,000,000 in view of excellent coating workability and coating film properties. From the viewpoint of excellent appearance such as leveling properties, the mass average molecular weight (Mw) is preferably in the range of 300,000 to 600,000.
- the molecular weight distribution (Mw / Mn) represented by the ratio to the number average molecular weight (Mn) is required to be 50 or more from the viewpoint of following the unevenness of the substrate and adhesion to various substrates. In particular, the range of 80 to 140 is preferable.
- the hydroxyl value of the oil-modified alkyd resin (A) is preferably in the range of 40 to 120, particularly in the range of 50 to 90, from the viewpoint of good adhesion to various substrates. preferable.
- various organic solvents may be added to the oil-modified alkyd resin (A).
- the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone, cyclic ethers such as tetrahydrofuran (THF) and dioxolane, esters such as methyl acetate, ethyl acetate, and butyl acetate, toluene, xylene Aromatics such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.
- ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone
- cyclic ethers such as tetrahydrofuran (THF) and dioxolane
- esters such as methyl acetate,
- the compound (B) having a (meth) acryloyl group used in the present invention is not particularly limited as long as it can react with the oil-modified alkyd resin (A) to obtain a cured coating film. From the viewpoint, it is preferably a compound having two or more (meth) acryloyl groups in one molecule.
- a (meth) acrylate monomer obtained by reacting a polyol and (meth) acrylic acid (2) Urethane (meth) acrylate obtained by adding a compound having a hydroxyl group and a (meth) acryloyl group to a compound having a terminal isocyanate group in the molecule, (3) At least two epoxy groups or glycidyl in the molecule Epoxy (meth) acrylate obtained by reacting a group-containing compound with (meth) acrylic acid, (4) polyol and polybasic acid Is a polyester (meth) acrylate obtained by reacting a polyester polyol obtained by condensation polymerization of the acid anhydride with (meth) acrylic acid, and (5) a copolymer acrylic polymer obtained by polymerizing an acrylic monomer or vinyl monomer with an acryloyl group. Examples thereof include acrylic acrylate obtained by pendant.
- the polyol is not particularly limited.
- (meth) acrylate monomers include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 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 di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) Chryrate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate
- examples of the compound having a terminal isocyanate group in the molecule include polyisocyanate or polyisocyanate exemplified as the polyol in the compound of (1) above. The thing obtained by making it react can be mentioned.
- the polyisocyanate in the above (2) may be, for example, any of aliphatic, alicyclic, aromatic and aromatic-aliphatic, such as For example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2 , 6-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyldi Socyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diiso
- Diisocyanates such as 3-dimethoxy-4.4'-diisocyanate diphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,10-decanmethylene diisocyanate, 1,3-cyclohexylene diisocyanate Nurates, burettes, adducts of these diisocyanates; triisocyanates such as 2,4,6-tolylene triisocyanate, 2,4,4′-triisocyanate diphenyl ether, etc. Can.
- Examples of the compound having a hydroxyl group and a (meth) acryloyl group in the above (2) include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, epoxy (meth) acrylate, 2-hydroxyethyl (meth).
- Examples of the compound having at least two epoxy groups or glycidyl groups in the molecule (3) include glycidyl ethers containing, for example, bisphenol A, bisphenol F, 2,6-xylenol, brominated bisphenol A, phenol novolac and the like.
- Type epoxy resin, glycidyl ester type epoxy resin containing dimer acid, glycidyl ester type epoxy resin containing aromatic or heterocyclic amine, alicyclic epoxy resin, acrylic resin having epoxy group or glycidyl group, etc. Can be mentioned.
- glycerol triglycidyl ether trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidyl ether, sorbitan tetraglycidyl ether, sorbitan pentaglycidyl ether , Triglycerol tetraglycidyl ether, tetraglycerol tetraglycidyl ether, pentaglycerol tetraglycidyl ether, triglycerol pentaglycidyl ether, tetraglycerol pentaglycidyl ether, pentaglycerol pentaglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl isocyanurate, etc. be able to
- examples of the polyol, polybasic acid or acid anhydride thereof include the same as those described above.
- the compound (B) having a (meth) acryloyl group the above (1) to (5) can be used, and these are polymerized due to the participation of the unsaturated bond contained therein.
- the reaction occurs and the active energy ray is cured, but if necessary, other compounds having an unsaturated bond such as diallyl fumarate and triallyl isocyanurate can also be contained.
- the mass ratio [(A) / (B)] of the content of the oil-modified alkyd resin (A) in the active energy ray-curable resin composition of the present invention and the compound (B) having a (meth) acryloyl group is:
- a range of 20/80 to 80/20 is preferable from the viewpoint of obtaining a coating film having good compatibility and a good coating film appearance.
- the range of 70/30 to 30/70 is more preferable in that an excellent adhesion to the substrate and a tough coating film can be obtained.
- a photopolymerization initiator (C) can be contained in order to favorably advance the curing reaction with active energy rays.
- the photopolymerization initiator (C) is not particularly limited as long as it generates radicals by the action of light, and specifically includes 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxy.
- Examples of the commercially available photopolymerization initiator (C) include Irgacure-184, 149, 261, 369, 500, 651, 754, 784, 819, 907, 1116, 1664, 1700, 1800, 1850, 2959, 4043, Darocur-1173, Lucillin TPO (manufactured by BASF), Kayacure-DETX, MBP, DMBI, EPA, OA (Nippon Kayaku Co., Ltd.) Company), BiCure-10, 55 (Stofa Chemical), Trigonal P1 (Akzo), Sandley 1000 (Sands), Deep (Apjon), Quantacure-PDO, ITX, EPD (manufactured by Ward Brenkinsop) and the like can be mentioned. These may be used alone or in combination of two or more.
- the photopolymerization initiator maintains light sensitivity satisfactorily and does not cause precipitation of crystals or deterioration of physical properties of the coating film.
- the range is preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass.
- an amino resin may be included as necessary to further improve the heat resistance of the resulting coating film.
- the amino resin examples include a methylolated amino resin synthesized from at least one of melamine, urea, and benzoguanamine and formaldehyde; such a methylolated amino resin, wherein a part or all of the methylol group is obtained.
- Alkyl etherified with a lower monohydric alcohol such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and the like.
- amino resins include, for example, Cymel 303 (manufactured by Nippon Cytec Industries, Inc., methylated melamine resin), Cymel 350 (manufactured by Nippon Cytec Industries, Inc., methylated melamine resin), Uban 520 (Mitsui).
- the amino resin when used, it is preferable to contain 5 to 20 parts by mass with respect to a total of 100 parts by mass of the oil-modified alkyd resin (A) and the compound (B) having a (meth) acryloyl group in the composition.
- composition of the present invention can contain a solvent in order to dilute and facilitate coating.
- the solvent is not particularly limited, but a low surface tension solvent is preferable in order to improve wettability.
- examples of such a solvent include alcohol solvents, ketone solvents, and the like.
- ethyl acetate, butyl acetate, toluene, xylene and the like can be used in combination in view of the evaporation rate and cost.
- composition of the present invention can contain a surface conditioner.
- the surface preparation agent is not particularly limited, and examples thereof include a fluorine-based additive and a cellulose-based additive.
- the fluorine-based additive has a function of preventing repelling when applied to various substrates by reducing surface tension and increasing wettability.
- Specific examples of the fluorine-based additive include Megafac F-177 (manufactured by DIC Corporation).
- the cellulosic additive has an effect of imparting a film-forming property at the time of coating.
- the cellulose additive is preferably a high molecular weight product having a number average molecular weight of 15000 or more in order to reduce fluidity. Examples of such a cellulose additive include cellulose-acetate-butyrate resin.
- the amount of the fluorine-based additive when the amount of the fluorine-based additive is increased, the adhesion of the deposited aluminum and the top coat is decreased, and when the amount of the cellulose-based additive is increased, the solid content of the composition of the present invention is increased. It is preferable to use a fluorine-based additive and a cellulose-based additive in combination.
- the addition amount of the surface preparation agent ranges from 0.01 to 3.0 parts by mass with respect to the total amount of fluorine-based additive and cellulose-based additive with respect to 100 parts by mass of the nonvolatile content in the composition. preferable.
- the fluorine-based additive is used alone, it is preferably in the range of 0.01 to 1.0 part by mass, and when the cellulose-based additive is used alone, it is 0.5 to 5.0 parts by mass. It is preferable that it is the range of these.
- the active energy ray-curable resin composition of the present invention further includes various additions such as a photosensitizer, an ultraviolet absorber, an antioxidant, a silicon-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent.
- a photosensitizer such as an ultraviolet absorber, an antioxidant, a silicon-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent.
- An agent may be contained.
- the active energy ray-curable resin composition of the present invention can be suitably used as an active energy ray-curable undercoat coating agent for metal deposition. Specifically, it is used as an undercoat layer when a metal vapor deposition layer is formed on a substrate.
- an undercoat layer when a metal vapor deposition layer is formed on a substrate.
- the active energy ray-curable resin composition of the present invention is applied onto a substrate by a method such as spray coating.
- the coating amount is preferably in the range of 5 to 60 ⁇ m after curing, and more preferably in the range of 10 to 40 ⁇ m.
- the resin composition is cured by irradiating active energy rays to form the undercoat layer.
- active energy rays include ultraviolet rays and electron beams.
- an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp as a light source can be used, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary.
- it is preferable to irradiate to ultraviolet integrated light quantity is 50 ⁇ 5000mJ / cm 2, accumulated light amount is more preferably irradiated such that the 500 ⁇ 2000mJ / cm 2.
- the base material on which the undercoat layer of the present invention is installed is provided with a metal vapor deposition layer thereon, and a top coat layer and the like are further provided thereon.
- the thickness of the metal vapor-deposited layer is preferably in the range of 30 nm to 3 ⁇ m
- the thickness of the topcoat layer after curing is preferably in the range of 3 to 40 ⁇ m.
- Examples of the molded body thus obtained include an automobile reflector.
- Mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
- Measuring device HLC-8220GPC manufactured by Tosoh Corporation Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation + Tosoh Corporation TSK-GEL SuperHZM-M ⁇ 4 Detector: RI (differential refractometer) Data processing; Multi-station GPC-8020 model II manufactured by Tosoh Corporation Measurement conditions; Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% tetrahydrofuran solution in terms of resin solids with a microfilter (100 ⁇ l)
- Synthesis example 1 In a flask equipped with a stir bar, temperature sensor, rectifying tube, decanter, soybean oil 380 parts, safflower oil 890 parts, p-tert-butylbenzoic acid 154 parts, pentaerythritol 472 parts, phthalic anhydride 754 parts, xylene 56 And 0.2 part of an organic titanium compound were charged, dry nitrogen was flowed into the flask and heated to 220 to 240 ° C. with stirring to perform a dehydration condensation reaction.
- alkyd resin (A1) an oil length 50 alkyd resin having a number average molecular weight of 4000, a mass average molecular weight of 530000, a hydroxyl value of 70, and an acid value of 12 was obtained. This is designated as alkyd resin (A1).
- Synthesis example 2 In a flask having a stir bar, temperature sensor, rectifying tube and decanter, 63 parts soybean oil, 1198 parts linseed oil, 560 parts pentaerythritol, 287 parts benzoic acid, 830 parts phthalic anhydride, 83 parts xylene and organotitanium compound 0 3 parts were charged, dry nitrogen was flowed into the flask and heated to 220-240 ° C. with stirring to conduct a dehydration condensation reaction. The reaction was stopped when the acid value became 10 mgKOH / g or less, and after cooling to 150 ° C., toluene and ethyl acetate were added dropwise to dilute to a solid content of 50%.
- alkyd resin (A2) an oil length 45 alkyd resin having a number average molecular weight of 3700, a mass average molecular weight of 300000, a hydroxyl value of 84, and an acid value of 10 was obtained. This is designated as alkyd resin (A2).
- Synthesis example 3 In a flask equipped with a stir bar, temperature sensor, rectifying tube and decanter, 750 parts of linseed oil, 600 parts of tall oil, 282 parts of pentaerythritol, 345 parts of trimethylolpropane, 314 parts of benzoic acid, 846 parts of phthalic anhydride, xylene 89 And 0.3 part of an organic titanium compound were charged, dry nitrogen was flowed into the flask and heated to 220 to 240 ° C. with stirring to perform a dehydration condensation reaction.
- alkyd resin (A3) an oil length 45 alkyd resin having a number average molecular weight of 3600, a mass average molecular weight of 410,000, a hydroxyl value of 51, and an acid value of 11 was obtained. This is designated as alkyd resin (A3).
- Acrylic resin (X) “Acridic 56-393-BA” (manufactured by DIC Corporation, 20 parts of styrene in 100 parts of monomer mixture, glass transition temperature: 5 ° C.) was used. This is designated as acrylic resin (X).
- Comparative Alkyd Resin (Y1) In a flask having a stir bar, a temperature sensor, and a condenser, “Beccosol OD-E-198-50” (DIC Corporation, oil length 28, using soybean oil as oil) 1000 And 0.7 part of isophorone diisocyanate were added, dry nitrogen was flowed into the flask and heated to 70 to 90 ° C. with stirring to carry out a urethanization reaction. The reaction was stopped when the isocyanate amount became 0.02% or less, and after cooling to 60 ° C., xylene was added dropwise to dilute to a solid content of 50%.
- alkyd resin (Y1) a urethane-modified alkyd resin having a number average molecular weight of 3,900, a mass average molecular weight of 170,000, and a molecular weight distribution (Mw / Mn) of 43.6 was obtained. This is designated as alkyd resin (Y1).
- Alkyd resin for comparison (Y2) “Beccosol 1323-60EL” (manufactured by DIC Corporation, oil length 28, using coconut oil as oil) was used. This is designated as alkyd resin (Y2).
- Alkyd resin for comparative example (Y3) In a flask having a stir bar, temperature sensor, rectifying tube, decanter, soybean oil 1412 parts, neopentyl glycol 259 parts, trimethylolpropane 445.6 parts, adipic acid 276 parts, phthalic anhydride 559 parts, xylene 90 parts and An organic titanium compound (0.3 parts) was charged, dry nitrogen was flowed into the flask, and heated to 220 to 240 ° C. with stirring to perform a dehydration condensation reaction.
- alkyd resin having an oil length of 50 having a number average molecular weight of 3,800, a mass average molecular weight of 310,000, a hydroxyl value of 78, and an acid value of 8 was obtained. This is designated as alkyd resin (Y3).
- alkyd resin having a number average molecular weight of 3,800, a mass average molecular weight of 303,000, a hydroxyl value of 41, and an acid value of 5.1 was obtained. This is designated as alkyd resin (Y4).
- Reflective Material BMC bulk molding compound
- PPS polyphenylene sulfide
- PBT polybutylene terephthalate
- PET polyethylene terephthalate
- PC polycarbonate
- the composition prepared previously was air spray-coated on the surface of each substrate. Thereafter, the solvent is dried under conditions of 80 ° C. ⁇ 10 minutes, and an undercoat layer having a film thickness of 10 to 15 ⁇ m is formed on the substrate by irradiating ultraviolet rays with an irradiation amount of 1000 mJ / cm 2 with an 80 W / cm high-pressure mercury lamp. Undercoat layer) was formed.
- Reflector 1 180 ° C
- Reflector 2 230 ° C
- Reflector 3 200 ° C
- Reflector 4 120 ° C
- the reflective plate 1 was evaluated for appearance and adhesion after being left in a constant temperature and humidity chamber with a temperature of 50 ° C. and a humidity of 95 RH% for 240 hours.
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Abstract
Description
質量平均分子量(Mw)、分子量分布(Mw/Mn)は下記条件のゲルパーミュレーションクロマトグラフィー(GPC)により測定した。
カラム ;東ソー株式会社製 TSK-GUARDCOLUMN SuperHZ-L
+東ソー株式会社製 TSK-GEL SuperHZM-M×4
検出器 ;RI(示差屈折計)
データ処理;東ソー株式会社製 マルチステーションGPC-8020modelII 測定条件 ;カラム温度 40℃
溶媒 テトラヒドロフラン
流速 0.35ml/分
標準 ;単分散ポリスチレン
試料 ;樹脂固形分換算で0.2%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
攪拌棒、温度センサー、精留管、デカンターを有するフラスコに、大豆油380部、サフラワー油890部、p-tert-ブチル安息香酸154部、ペンタエリスリトール472部、無水フタル酸754部、キシレン56部及び有機チタン化合物0.2部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら220~240℃に加熱し、脱水縮合反応を行った。酸価が12mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、トルエンと酢酸エチルを滴下して固形分50%に希釈した。その結果、数平均分子量4000、質量平均分子量530000、水酸基価70、酸価12である油長50のアルキド樹脂を得た。これをアルキド樹脂(A1)とする。
攪拌棒、温度センサー、精留管、デカンターを有するフラスコに、大豆油63部、亜麻仁油1198部、ペンタエリスリトール560部、安息香酸287部、無水フタル酸830部、キシレン83部及び有機チタン化合物0.3部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら220~240℃に加熱し、脱水縮合反応を行った。酸価が10mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、トルエンと酢酸エチルを滴下して固形分50%に希釈した。その結果、数平均分子量3700、質量平均分子量300000、水酸基価84、酸価10である油長45のアルキド樹脂を得た。これをアルキド樹脂(A2)とする。
攪拌棒、温度センサー、精留管、デカンターを有するフラスコに、亜麻仁油750部、トール油600部、ペンタエリスリトール282部、トリメチロールプロパン345部、安息香酸314部、無水フタル酸846部、キシレン89部及び有機チタン化合物0.3部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら220~240℃に加熱し、脱水縮合反応を行った。酸価が13mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、トルエンと酢酸エチルを滴下して固形分50%に希釈した。その結果、数平均分子量3600、質量平均分子量410000、水酸基価51、酸価11である油長45のアルキド樹脂を得た。これをアルキド樹脂(A3)とする。
「アクリディック 56-393-BA」(DIC株式会社製、単量体混合物100部中スチレン20部、ガラス転移温度:5℃)を用いた。これをアクリル樹脂(X)とする。
攪拌棒、温度センサー、コンデンサを有するフラスコに、「ベッコゾール OD-E-198-50」(DIC株式会社製、油長28、油脂として大豆油を使用)を1000部、イソホロンジイソシアネート0.7部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら70~90℃に加熱し、ウレタン化反応を行った。イソシアネート量が0.02%以下となったところで反応を停止し、60℃まで冷却後、キシレンを滴下して固形分50%に希釈した。その結果、数平均分子量3,900、質量平均分子量170,000、分子量分布(Mw/Mn)43.6であるウレタン変性アルキド樹脂を得た。これをアルキド樹脂(Y1)とする。
「ベッコゾール 1323-60EL」(DIC株式会社製、油長28、油脂としてヤシ油を使用)を用いた。これをアルキド樹脂(Y2)とする。
攪拌棒、温度センサー、精留管、デカンターを有するフラスコに、大豆油1412部、ネオペンチルグリコール259部、トリメチロールプロパン445.6部、アジピン酸276部、無水フタル酸559部、キシレン90部及び有機チタン化合物0.3部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら220~240℃に加熱し、脱水縮合反応を行った。酸価が8mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、トルエンと酢酸エチルを滴下して固形分50%に希釈した。その結果、数平均分子量3,800、質量平均分子量310,000、水酸基価78、酸価8である油長50のアルキド樹脂を得た。これをアルキド樹脂(Y3)とする。
攪拌棒、温度センサー、精留管、デカンターを有するフラスコに、亜麻仁油1269部、ペンタエリスリトール593部、無水フタル酸880g、キシレン60部及び有機チタン化合物0.3部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら220~240℃に加熱し、脱水縮合反応を行った。酸価が5.1mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、トルエンと酢酸エチルを滴下して固形分50%に希釈した。その結果、数平均分子量3,800、質量平均分子量303,000、水酸基価41、酸価5.1である油長45のアルキド樹脂を得た。これをアルキド樹脂(Y4)とする。
表1に示す固形分比率(質量比)で混合し、液状の組成物を調製した。組成物を調整する際に用いた原料は以下の通りである。
ユニディックV-4025:ウレタンアクリレート(DIC株式会社製)
カヤラッドDPHA:ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(日本化薬株式会社製)
アロニックスM-305:ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物(東亞合成株式会社製)
NK-エステルAPG-200:トリプロピレングリコールジアクリレート(新中村化学工業製)
サイメル303:メラミン樹脂(日本サイテックインダストリーズ株式会社製)
サイメル307:メラミン樹脂(日本サイテックインダストリーズ株式会社製)
イルガキュア651:光重合開始剤(BASF社製)
カヤキュアDETX-S:光重合開始剤(日本化薬株式会社製)
イルガキュア184:光重合開始剤(BASF社製製)
メガファックF-477:表面改質剤(DIC株式会社製)
得られた組成物を40℃で3カ月間保存し、その貯蔵安定性を目視にて観察し、以下に示す評価基準にて評価した。結果を表1に示した。
○:粘度変化がほとんど無く、ゲルが発生していない。
△:粘度の上昇は見られるが、ゲルは発生しておらず、塗装可能である。
×:粘度の上昇が著しく塗装不可能であるか、またはゲルが発生している。
基材として、BMC(バルクモールディングコンパウンド)、PPS(ポリフェニレンサルファイド)、PBT(ポリブチレンテレフタレート)/PET(ポリエチレンテレフタレート)アロイ、PC(ポリカーボネート)を用いた。
反射板の平滑性について、以下の評価基準にて目視で評価した。
〇:液タレやユズ肌が見られず、平滑である。
△:わずかに液タレやユズ肌見られるが、使用可能な範囲である。
×:明らかに液タレやユズ肌が見られる。
反射板の外観状態について、以下の評価基準にて目視で評価した。
○:クラックやフクレ、白化等の欠陥がない。
△:僅かにクラックやフクレ、白化等の欠陥がある。
×:はっきりとクラックやフクレ等の欠陥がある。
反射板の保護膜上に、2mm幅で10×10の碁盤目状にカッターナイフで切れ目を入れ、その上からセロハン粘着テープを貼着した後、急速に剥がす操作を行い、剥離せずに残存した碁盤目の数を数え、以下の評価基準にて評価した。
○:碁盤目の残存数が100個。
△:碁盤目の残存数が91~99個。
×:碁盤目の残存数が90個以下。
反射板1~4を以下の温度の熱風乾燥炉に入れ、96時間放置した後の、外観状態、密着性について評価した。
反射板1:180℃
反射板2:230℃
反射板3:200℃
反射板4:120℃
反射板1を温度50℃、湿度95RH%の恒温恒湿器の中で240時間放置した後の、外観状態、密着性について評価した。
Claims (8)
- 油変性アルキド樹脂(A)と、(メタ)アクリロイル基を有する化合物(B)とを含有する活性エネルギー線硬化型樹脂組成物であって、
前記油変性アルキド樹脂(A)が、ヨウ素価が100以上の油脂(a1)を2種以上併用して得られる、油長が30~60、質量平均分子量が20万~100万、分子量分布(Mw/Mn)が50以上の油変性アルキド樹脂であることを特徴とする活性エネルギー線硬化型樹脂組成物。 - 前記ヨウ素化が100以上の油脂(a1)が、亜麻仁油、大豆油、サフラワー油及びトール油からなる群から選ばれる油脂である請求項1記載の活性エネルギー線硬化型樹脂組成物。
- 前記油変性アルキド樹脂(A)が、更に分子内に水酸基を3個以上有する分岐アルカン型ポリオール(a2)と、分子内に環状不飽和基を有する多塩基酸(a3)とを用いて得られるものである請求項1又は2記載の活性エネルギー線硬化型樹脂組成物。
- 前記(メタ)アクリロイル基を有する化合物(B)が、(メタ)アクリレートモノマー、ウレタン(メタ)アクリレート、エポキシ(メタ)アクリレート、ポリエステル(メタ)アクリレート及びアクリルアクリレートからなる群から選ばれる1種以上の化合物である請求項1~3の何れか1項記載の活性エネルギー線硬化型樹脂組成物。
- 前記油変性アルキド樹脂(A)と、前記(メタ)アクリロイル基を有する化合物(B)との質量比〔(A)/(B)〕が20/80~80/20の範囲である請求項1~4の何れか1項記載の活性エネルギー線硬化型樹脂組成物。
- 更に光重合開始剤(C)を含有する請求項1~5の何れか1項記載の活性エネルギー線硬化型樹脂組成物。
- 請求項1~6の何れか1項記載の活性エネルギー線硬化型樹脂組成物を含んでなることを特徴とする金属蒸着用活性エネルギー線硬化型下塗り用コーティング剤。
- 請求項7記載の下塗り用コーティング剤からなるアンダーコート層を有することを特徴とする成形体。
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JP2014542609A JP5692624B1 (ja) | 2013-07-02 | 2014-06-17 | 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体 |
CN201480008716.4A CN105189568B (zh) | 2013-07-02 | 2014-06-17 | 活性能量射线固化型树脂组合物、含有其的底涂用涂布剂及成型体 |
US14/760,013 US9512330B2 (en) | 2013-07-02 | 2014-06-17 | Actinic-radiation-curable resin composition, primer containing the same, and shaped article |
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JP2017039791A (ja) * | 2015-08-17 | 2017-02-23 | Dic株式会社 | 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体 |
JP2019167508A (ja) * | 2018-03-26 | 2019-10-03 | 三菱ケミカル株式会社 | 活性エネルギー線硬化性組成物及び金属成形物 |
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EP3428206B1 (en) * | 2016-03-10 | 2021-06-23 | DIC Corporation | Curable composition comprising an acrylic-modified alkyd resin and coating material for priming for thin inorganic film |
TWI724177B (zh) * | 2016-07-14 | 2021-04-11 | 日商迪愛生股份有限公司 | 活性能量線硬化型樹脂組成物及金屬薄膜用底塗劑 |
CN110225932B (zh) * | 2017-01-25 | 2021-11-19 | Dic株式会社 | 活性能量射线固化型水性树脂组合物及无机材料薄膜用底涂剂 |
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CN105189568A (zh) | 2015-12-23 |
US9512330B2 (en) | 2016-12-06 |
JPWO2015001949A1 (ja) | 2017-02-23 |
JP5692624B1 (ja) | 2015-04-01 |
US20150361298A1 (en) | 2015-12-17 |
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