TW202233774A - Active energy ray-curable undercoat composition for FRP - Google Patents

Abstract

The purpose of the present invention is to provide an undercoat composition that can be cured by active energy rays even if almost no xylene is used as a solvent. The present invention provides an active energy ray-curable undercoat composition for FRP for carrying out metal deposition, said composition containing a polyfunctional (meth)acrylate (A) and an oil-modified alkyd resin (B), wherein: the polyfunctional (meth)acrylate (A) has two or more (meth)acryloyl groups per molecule, and is contained in an amount of 55-85 parts by mass relative to a total amount of 100 parts by mass of the polyfunctional (meth)acrylate (A) and the oil-modified alkyd resin (B); the oil-modified alkyd resin (B) is contained in an amount of 15-45 parts by mass relative to a total amount of 100 parts by mass of the polyfunctional (meth)acrylate (A) and the oil-modified alkyd resin (B); and the oil-modified alkyd resin (B) has an oil length of 35-50%, an acid value of 0.01-10 mg KOH/g, a hydroxyl value of 80-130 mg KOH/g, and a weight average molecular weight of 80,000-150,000.

Description

Active energy ray hardening primer composition for FRP

The present invention relates to an active energy ray-curable primer coating composition for FRP for metal vapor deposition.

From the viewpoint of light weight and excellent corrosion resistance, heat resistance, and impact resistance, reflector members such as automotive lamps are often used by mirroring the surface of fiber reinforced plastic (hereinafter also referred to as "FRP"). Fiber-reinforced plastics are PPS (polyphenylene sulfide), PPE (polyphenylene ether), PBT (polybutylene terephthalate)/PET (polyethylene terephthalate) reinforced with fillers such as glass fiber, etc. Alloy resin, heat-resistant PC (polycarbonate), ABS (acrylonitrile-butadiene-styrene copolymer resin), PMMA (acrylic resin), etc. As for the method of forming a mirror surface on FRP, there are generally methods of vapor deposition or sputtering of metals such as aluminum, but it is difficult to obtain a smooth material surface due to segregation of fibers, air bubbles mixed in, etc. A method of obtaining a mirror surface by coating the surface with a primer coating and performing metal evaporation after hardening.

In addition to heat resistance to light bulbs, engines, sunlight, etc., the primer used for this purpose also requires heat resistance to the heat source of molten metal in the vacuum evaporation and sputtering steps, and heat resistance to the heat source of the molten metal directly under the high temperature state. The heat resistance of the metal that hits the coating film and adheres to it, and has been using active energy ray hardening type coatings with excellent coating film hardness and the like.

Oil-modified alkyd resins have been formulated in the above-mentioned primers for a long time, which can take into account the adhesion to the non-uniform material surface of fiber segregation and the adhesion to the vapor-deposited metal, as well as corrosion resistance, heat resistance and repeated cold and heat. Excellent resistance. Oil-modified alkyd resins are produced by dehydration condensation reaction of monofunctional fatty acids such as soybean oil, difunctional or higher acids such as phthalic acid, or their acid anhydrides, and ethylene glycol or other alcohols. The solvent used for the dehydration condensation reaction needs to have low solubility of water and a boiling point suitable for the dehydration condensation reaction temperature, and xylene (a mixture of ortho, meta, para and ethylbenzene, etc.) has been generally used. In addition, since xylene can also be used as a thinner for paints, it can be used without desolvation or solvent substitution.

However, xylenes, along with benzene and toluene, are harmful substances that affect the human body and aquatic organisms. In recent years, the application range of paints containing more than a fixed amount of xylene has been severely restricted. Some attempts have been made to manufacture alkyd resins by using a solvent instead of xylene. However, because the solvent is not suitable as a thinner for paints, the paint workability and appearance are deteriorated. In addition, some people have tried to use xylene to remove the solvent, but there are the following problems: the energy consumption for solvent removal is large, the stability of the alkyd resin after solvent removal is deteriorated, and the storage stability is reduced. Although some people have also developed an active energy ray-curable primer coating composition for FRP for metal vapor deposition without using alkyd resin, the reflector member of automobile lamps is a combination of various materials. There is not much room for material selection.

In recent years, with the continuous increase in the use of LED bulbs as the light source of automobile lamps, such as integrating the direction indicator function into the interior of the lamp, the shape of the reflecting member has gradually become more complex and electronic devices. After the above-mentioned components are painted, poor drying and film thickness are likely to occur due to different parts. Therefore, a paint with better solvent removal properties and a wider allowable range of film thickness is required than conventional paints. From the viewpoint of energy saving and environmental protection, the preheating of the desolvation step before UV irradiation also needs to be reduced in temperature and in a short time, but it is limited by the high boiling point of xylene.

Filaments or HID-type bulbs used in automotive lamps in the past emit a lot of heat energy while generating light, so even if water seeps into the interior of the lamps when it rains or when the car is washed, the interior space will remain dry by using the lamps. Although LED bulbs are rapidly becoming popular, they do not generate heat in the direction of light emission and cannot remove the moisture in the interior space of the lamp, so it is necessary to improve the moisture resistance of the coating film.

In addition, from the viewpoint of lightweighting of automobiles, FRP parts are gradually becoming lighter. Conventionally, unsaturated polyester resins (BMC: bulk molding compound) are mostly used, but PPE (polyphenylene ether), PBT (polybutylene terephthalate)/PET (polyethylene terephthalate) alloy resin, PC (polycarbonate), ABS (acrylonitrile-butadiene-styrene copolymer resin), PMMA ( FRP such as acrylic resin) is increasing. PPE (polyphenylene ether), PBT (polybutylene terephthalate)/PET (polyethylene terephthalate) alloy resin, PC (polycarbonate), ABS (acrylonitrile-butadiene-benzene) Materials such as ethylene copolymer resin) and PMMA (acrylic resin) are prone to a phenomenon called "outgassing", which is a phenomenon in which the unreacted raw materials and water remaining in the material manufacturing volatilize over time, not only in the drying step after painting. , Outgassing will occur in the vacuum evaporation step, and outgassing will also occur after assembling in the car. If outgassing occurs under the primer coating, the mirror surface may deteriorate due to peeling or destruction of the coating film. The high humidity of the interior space of the lamps brought about by the increase of LED bulbs, coupled with the increase of materials with a lot of outgassing, will require a primer coating with high temperature and humidity cycle resistance.

Patent Document 1 (WO1995/032250) describes a liquid composition for a UV-curable primer for metal vapor deposition for FRP, which contains a compound having at least two (meth)acryloyl groups and an oil-modified alkyd resin , but this composition requires xylene as a diluent, so it cannot be used for the purpose of restricting the use of xylene. When the composition using the alkyd resin disclosed in Patent Document 1 is applied to a reflection member of an automobile lamp for an LED light bulb, since a large amount of high-boiling xylene is contained, it is easy to preheat and dry a member with a complicated shape. During the step, the poorly ventilated parts or the thick film parts have whitening caused by poor drying or poor mirror surface after evaporation. The coating composition of Patent Document 1 has a high hydroxyl value of the alkyd resin, so from the viewpoint of solubility and storage stability, a polyfunctional (meth)acrylate having a high hydroxyl value is deliberately prepared. The hydroxyl groups in the composition do not contribute to the UV curing reaction, so many hydroxyl groups remain in the cured coating film. As a result, the cured coating film of the coating composition of Patent Document 1 is prone to problems such as peeling in a humidity resistance test and a temperature and humidity cycle test simulating a closed space inside an automobile lamp.

prior art literature Patent Literature Patent Document 1: WO1995/032250

The problem to be solved by the invention An object of the present invention is to provide an active energy ray-curable primer composition for FRP for metal vapor deposition, which improves the primer composition of Patent Document 1 and is effective against outgassing Duozhi Material is designed as a reflective component for automotive lamps and lanterns for LED bulbs, using oil-modified alkyd resin that does not contain xylene as much as possible, and improves adhesion, energy saving, environmental protection, and temperature and humidity cycle resistance.

means of solving problems In order to solve the above-mentioned problems, the present invention provides the following aspects. [1] An active energy ray-curable primer coating composition for FRP for metal vapor deposition, comprising a polyfunctional (meth)acrylate (A) and an oil-modified alkyd resin (B); The polyfunctional (meth)acrylate (A) has two or more (meth)acryloyl groups in the molecule, and is modified with respect to the polyfunctional (meth)acrylate (A) and the oil-modified alkyd The total amount of resin (B) is 100 parts by mass, and the polyfunctional (meth)acrylate (A) is contained in an amount of 55 to 85 parts by mass; and, The oil-modified alkyd resin (B) is contained in an amount of 15 to 45 parts by mass relative to 100 parts by mass of the total amount of the polyfunctional (meth)acrylate (A) and the oil-modified alkyd resin (B). ), and the aforementioned oil-modified alkyd resin (B) has an oil length of 35 to 50%, an acid value of 0.01 to 10 mgKOH/g, a hydroxyl value of 80 to 130 mgKOH/g, and a weight average molecular weight of 80,000 to 150,000. [2] The active energy ray-curable primer coating composition for FRP for metal vapor deposition according to [1], wherein the oil-modified alkyd resin (B) is modified by the following oils and fats : At least one selected from the group consisting of pine oil, soybean oil, safflower oil, linseed oil, tung oil, castor oil and mixtures of these oils and fats. [3] The active energy ray-curable primer coating composition for metal vapor deposition for FRP according to [1] or [2], wherein the oil-modified alkyd resin (B) is modified and used The oil and fat component (b) of the product has an iodine value of 80 to 160 alone or after mixing two or more kinds of fats and oils. [4] The active energy ray-curable primer coating composition for FRP for metal vapor deposition according to any one of [1] to [3], wherein the above-mentioned active energy ray-curable primer coating composition is further The photopolymerization initiator (C) is blended in an amount of 1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). [5] The active energy ray-curable primer coating composition for FRP for metal vapor deposition according to any one of [1] to [4], wherein the active energy ray-curable primer coating composition further comprises : At least one selected from the group consisting of surface conditioners, ultraviolet absorbers, light stabilizers, antioxidants, storage stabilizers, adhesion imparting agents, and mixtures thereof. [6] The active-energy-ray-curable primer coating composition for FRP for metal vapor deposition according to any one of claims 1 to 5, wherein the active-energy-ray-curable primer coating composition further comprises: At least one selected from the group consisting of organic pigments, inorganic pigments, organic beads, inorganic beads and mixtures thereof.

Invention effect The present invention provides an active energy ray hardening primer coating composition for FRP used for metal evaporation. The primer coating composition is stable in storage and coating appearance even if the xylene content in the coating formulation is less than 1%. Still excellent. In the present invention, the oil-modified alkyd resin is adjusted to an oil length of 35-50%, an acid value of 0.01-10 mgKOH/g, a hydroxyl value of 80-130 mgKOH/g, and a weight-average molecular weight of 80,000-150,000, which can greatly reduce the two Toluene content.

In addition, the present invention is a primer coating, which is applied to materials (PPS (polyphenylene sulfide), PPE (polyphenylene ether), PBT (polybutylene terephthalate)/PET ( Polyethylene terephthalate) alloy resin, heat-resistant PC (polycarbonate), ABS (acrylonitrile-butadiene-styrene copolymer resin), PMMA (acrylic resin)) reflection member, can reduce or prevent Defects caused by outgassing, and will also improve other properties, adhesion, energy saving, environmental protection, temperature and humidity cycle resistance.

Form for carrying out the invention The above-mentioned active energy ray hardening primer for FRP is an active energy ray hardening primer composition comprising a polyfunctional (meth)acrylate (A) and an oil-modified alkyd resin (B). base) Acrylate (A) has two or more (meth)acryloyl groups in the molecule, and is relative to the total amount of polyfunctional (meth)acrylate (A) and oil-modified alkyd resin (B) 100 parts by mass, containing the polyfunctional (meth)acrylate (A) in an amount of 55 to 85 parts by mass, and relative to the polyfunctional (meth)acrylate (A) and the oil-modified alkyd resin The total amount of (B) is 100 parts by mass, and the oil-modified alkyd resin (B) is contained in an amount of 15 to 45 parts by mass, and the oil-modified alkyd resin (B) has an oil length of 35 to 50%, an acid The value is 0.01~10mgKOH/g, the hydroxyl value is 80~130mgKOH/g and the weight average molecular weight is 80,000~150,000.

Polyfunctional (meth)acrylate (A) Component (A) of the active energy ray-curable paint primer composition of the present invention is a polyfunctional (meth)acrylate having at least two (meth)acryloyl groups in the molecule. In the present invention, the above-mentioned polyfunctional (meth)acrylate is polymerized by ultraviolet irradiation and the action of a photopolymerization initiator, and after curing, a primer coating film is formed.

Examples of the polyfunctional (meth)acrylate (A) include (a) those obtained by reacting a polyhydric alcohol with (meth)acrylic acid, and (b) compounds having a terminal isocyanate group in the molecule, added with Urethane acrylate etc. obtained from the compound of hydroxyl group and (meth)acryloyl group.

(a) One obtained by reacting a polyhydric alcohol with (meth)acrylic acid, specifically, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol Di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylene glycol di(meth)acrylate , polypropylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-Pentanediol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, 1,2-Hexanediol di(meth)acrylate di(meth)acrylate, 1,6 -Hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate (meth)acrylate, cyclohexanediol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, hydrogenated bisphenol AF di(meth)acrylate base) acrylate, hydroxytrimethylacetate, neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tricyclodecane Alkane dimethanol di(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]perylene diacrylate, glycerol tri(meth)acrylate, diglycerol tri(methyl) ) acrylate, 1,2,6-hexanetriol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2, 5-Pentanetriol tri(meth)acrylate, 3-(2-hydroxyethoxy)-1,2-propanediol tri(meth)acrylate , neotaerythritol tri(meth)acrylate, ginseng(2-(meth)acryloyloxyethyl)trimeric isocyanate, neotaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra (Meth)acrylate, Dipiveaerythritol tetra (meth)acrylate, Dipiveaerythritol penta (meth)acrylate, Dipiveaerythritol hexa (meth)acrylate. These polyfunctional (meth)acrylates (A) may be used alone or in combination of two or more.

In (b) urethane-type polyfunctional (meth)acrylate (A) obtained by adding a compound having a terminal isocyanate group to a compound having a hydroxyl group and a (meth)acryloyl group in the molecule (A), in the molecule The compound having a terminal isocyanate group in it may be, for example, the following: isophorone diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate Isocyanates, 1,3-bis(isocyanatomethyl)cyclohexane (cis-, trans-mixed) and cyanurate-type trimers of these. Examples of the hydroxyl group-containing (meth)acrylate compound include hydroxyethyl (meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and neotaerythritol. Tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipivalerythritol penta(meth)acrylate, and the like. The urethane (meth)acrylate (A) may be used alone or in combination of two or more hydroxyl-containing (meth)acrylate compounds so that the average number of functional groups in the molecule may be 2 or more.

The primer coating composition of the present invention contains 55 to 85 parts by mass of the above-mentioned polyfunctional ( Meth)acrylate (A). If it is less than 55 parts by mass, the repeated heat resistance and repeated moisture resistance will be inferior, and if it is more than 85 parts by mass, the adhesiveness will be reduced, so it is limited to the above range. And it should be 60-80 mass parts.

Oil modified alkyd resin (B) The component (B) of the present invention is an oil-modified alkyd resin. The above-mentioned oil-modified alkyd resin (B) can impart adhesion to FRP. The oil-modified alkyd resin (B) used in the present invention must have an oil length of 35-50%, an acid value of 0.01-10 mgKOH/g, a hydroxyl value of 80-130 mgKOH/g, and a weight average molecular weight of 80,000-150,000.

The above-mentioned oil-modified alkyd resin can be obtained by using a polyhydric alcohol and a polybasic acid or an acid anhydride thereof, and further using a fat or oil fatty acid as a modifier.

The polyhydric alcohol used for the oil-modified alkyd resin is not particularly limited, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, trimethylene glycol, polyethylene glycol Propylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol Alcohol, 1,2-hexanediol, 1,6-hexanediol, heptanediol, 1,10-decanediol, cyclohexanediol, 2-butene-1,4-diol, 3-cyclo Hexene-1,1-dimethanol, 4-methyl-3-cyclohexene-1,1-dimethanol, 3-methylene-1,5-pentanediol, (2-hydroxyethoxy) -1-Propanol, 4-(2-hydroxyethoxy)-1-butanol, 5-(2-hydroxyethoxy)-pentanol, 3-(2-hydroxypropoxy)-1-butanol alcohol, 4-(2-hydroxypropoxy)-1-butanol, 5-(2-hydroxypropoxy)-1-pentanol, 1-(2-hydroxyethoxy)-2-butanol, 1-(2-hydroxyethoxy)-2-pentanol, hydrogenated bisphenol A, glycerol, diglycerol, polycaprolactone, 1,2,6-hexanetriol, trimethylolpropane, trimethylolethyl Alkane, pentanetriol, paramethylolamine methane, 3-(2-hydroxyethoxy)-1,2-propanediol, 3-(2-hydroxypropoxy)-1,2-propanediol, 6-( 2-Hydroxyethoxy)-1,2-hexanediol, 1,9-nonanediol, 1,10-decanediol, hydroxytrimethylacetate neopentyl glycol, spiroglycerol, 2,2-bis (4-Hydroxyethoxyphenyl)propane, 2,2-bis(4-hydroxypropoxyphenyl)propane, Neopentaerythritol, Dipionaerythritol, Trinepentaerythritol, Trimethylolpropane , ditrimethylolpropane, trimethylolpropane, bis(2-hydroxyethyl)-trimeric isocyanate, bis(2-hydroxyethyl)-1-acetoxyethyl isocyanate, bis(2-hydroxyethyl)- Polyols such as 2-acetyloxyethyl isocyanate, mannitol, and glucose; in addition, ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone, etc. can also be used for these polyols. Alkylene oxide-modified or lactone-modified polyols obtained by addition reaction; polyester polyols with terminal hydroxyl groups obtained by condensing excess of these polyols with polybasic acids or their anhydrides ether polyols, etc.

The polybasic acid or its anhydride is not particularly limited, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, methylcyclohexene tricarboxylic acid, adipic acid, sebacic acid, and azelaic acid. , tetrahydrophthalic acid, hexahydrophthalic acid, himic acid, succinic acid, dodecylsuccinic acid, methylglutaric acid, pimelic acid, malonic acid, maleic acid, fumaric acid, chlorine Maleic acid, dichloromaleic acid, citraconic acid, mesaconic acid, itaconic acid, tetrahydrophthalic acid, carbic acid, HET acid, aconitic acid, glutaric acid , such anhydrides, etc.

The fat or oil fatty acid used as the modifier is not particularly limited, and may be any of non-drying oil, semi-drying oil, and drying oil, and preferably has an iodine value of 80 to 160. For example, the above-mentioned thing is selected from the group which consists of pine oil, soybean oil, safflower oil, linseed oil, tung oil, castor oil, and mixtures of these oils and fats. The iodine value is expressed in grams of iodine that can be added to 100 g of fat and oil, which means that the number of double bonds in the fatty acid in the sample is large. If the iodine value is less than 80, the compatibility with the polyfunctional (meth)acrylate having a double bond will decrease, the appearance will deteriorate, the ultraviolet curability will decrease, and the moisture resistance and heat resistance will also decrease. If it exceeds 160, the dry oil component will increase, and the storage stability of the alkyd resin and the composition will therefore decrease.

In the present invention, the oil length of the above-mentioned oil-modified alkyd resin must be 35-50%. The so-called "oil length" is a value representing the oil content based on a weight percentage. If the oil length is less than 35%, the viscosity of the alkyd resin will increase, and the coating appearance will be deteriorated and cannot be processed into a mirror surface. In addition, when the oil length exceeds 50%, the viscosity of the alkyd resin will decrease, so that the liquid sags after painting and the appearance deteriorates.

The oil-modified alkyd resin (B) used in the present invention must have an acid value in the range of 0.01 to 10 mgKOH/g. If the acid value is less than 0.01 mgKOH/g, the reaction will proceed until almost the end of the reaction, which will take time and reduce productivity. If it exceeds 10 mgKOH/g, the storage stability of the oil-modified alkyd resin and the composition will decrease, and the water resistance and moisture resistance of the coating film will decrease. The acid value is preferably 1 to 7 mgKOH/g, and preferably 2 to 5 mgKOH/g.

The oil-modified alkyd resin (B) must have a weight average molecular weight of 80,000 to 150,000. The weight average molecular weight is measured by gel permeation chromatography (GPC). If the weight-average molecular weight is less than 80,000, the film-forming property of the coating film is lowered and the defects of the FRP material cannot be shielded, so that the appearance is deteriorated and the heat resistance is lowered. If it exceeds 150,000, it will become high viscosity, and it will become difficult to obtain a smooth coating film plane, an external appearance will deteriorate, and it will not be able to be processed into a mirror surface after vapor deposition. The weight average molecular weight is preferably 90,000 to 130,000, and preferably 100,000 to 120,000.

The primer coating composition of the present invention contains 15 to 45 parts by mass of the above-mentioned oil-modified oil based on 100 parts by mass of the total of the polyfunctional (meth)acrylate (A) and the oil-modified alkyd resin (B). Alkyd resin (B). If the oil-modified alkyd resin (B) is less than 15 parts by mass, the adhesiveness will decrease, and if it is more than 45 parts by mass, the repeated heat resistance and the repeated moisture resistance will be inferior. The oil-modified alkyd resin (B) is preferably 20 to 35 parts by mass.

、2,4-二異丙基-9-氧硫𠮿

、2,4-二乙基-9-氧硫𠮿

、2-氯-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

、2,2-二甲氧基-2-苯基苯乙酮、α,α-二氯-4-苯氧丙酮、對三級丁基三氯苯乙酮、對三級丁基二氯苯乙酮、2,2-二乙氧基苯乙酮、對二甲胺基苯乙酮、羥基環己基苯基酮、1-(4-異丙苯基)-2-羥基-2-甲基丙-1-酮、2,2-二甲氧基-1,2-二苯基乙-1-酮、2,4,6-三甲基苯偶姻氧化二苯膦、2-甲基-1-[4-(甲硫基)苯基]-2-嗎福林基丙-1-酮、4-(2-丙烯醯氧基)氧基乙氧基苯基-2-羥基-2-丙基酮、4-(2-羥基)苯基-(2-羥基-2-丙基)酮、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基氧化苯膦。在該等之中，宜為2,4-二甲基-9-氧硫

、2,4-二異丙基-9-氧硫

、2,4-二乙基-9-氧硫

、2-氯-9-氧硫

、2-異丙基-9-氧硫

、羥基環己基苯基酮、1-(4-異丙苯基)-2-羥基-2-甲基丙-1-酮、2,2-二甲氧基-1,2-二苯基乙-1-酮。在本發明中，可使用該等中之1種或將2種以上組合來使用。 Photopolymerization Initiator (C) The active energy ray curable primer composition of the present invention further incorporates a photopolymerization initiator (C) to impart active energy ray curability. The photopolymerization initiator (C) is not particularly limited, and examples thereof include the following: benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, Benzoin, α-methylbenzoin, benzoin n-butyl ether, 2-ethylanthraquinone, 2-tertiary butylanthraquinone, 1-chloroanthraquinone, 2-aminoanthraquinone, 2 -Aminoanthraquinone, benzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, benzophenone methyl ether, methyl benzophenone, 4,4-dichlorodiphenyl Phenyl ketone, 4,4-bis-diethylamino diphenyl ketone, diphenyl sulfide, Tetramethylthiuram disulfide, 2,4-dimethyl-9-oxysulfur 𠮿

, 2,4-diisopropyl-9-oxothio

, 2,4-diethyl-9-oxothio

, 2-chloro-9-oxysulfur

, 2-isopropyl-9-oxothio

, 2,2-dimethoxy-2-phenylacetophenone, α,α-dichloro-4-phenoxyacetone, p-tertiary butyl trichloroacetophenone, p-tertiary butyl dichlorobenzene Ethanone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoin diphenylphosphine oxide, 2-methyl- 1-[4-(Methylthio)phenyl]-2-morpholinylpropan-1-one, 4-(2-propenyloxy)oxyethoxyphenyl-2-hydroxy-2- Propyl ketone, 4-(2-hydroxy)phenyl-(2-hydroxy-2-propyl) ketone, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl phenylphosphine oxide. Among these, 2,4-dimethyl-9-oxothioate is preferred

, 2,4-diisopropyl-9-oxothio

, 2,4-diethyl-9-oxothio

, 2-chloro-9-oxosulfur

, 2-isopropyl-9-oxothio

, hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethyl -1-keto. In the present invention, one or more of these can be used in combination.

The active energy ray-curable primer composition of the present invention contains 1 to 15 parts by mass based on 100 parts by mass in total of the polyfunctional (meth)acrylate (A) and the oil-modified alkyd resin (B). The said photoinitiator (C) is comprised. If it is less than 1 part by mass, active energy ray curing cannot be performed, and adhesion, water resistance, moisture resistance, and heat resistance are poor, and if it is more than 15 parts by mass, unreacted photopolymerization initiator remains after active energy ray irradiation On the other hand, as a plasticizer, there is a disadvantage that water resistance, moisture resistance, heat resistance, and the like are lowered. The photopolymerization initiator (C) is preferably 3 to 10 parts by mass.

other ingredients In the present invention, in addition to the above-mentioned components, a solvent, a surface conditioner, and the like may be further added. The above-mentioned solvent has the effect of diluting the base coating composition of the present invention so that it can be easily applied.

Although it does not specifically limit as said solvent, For example, an alcohol type solvent, a ketone type solvent, an ester type solvent, a petroleum type solvent, etc. are mentioned. In order to improve wettability, toluene, xylene, etc. may be used in combination, but it is preferable not to use these as much as possible in the active energy ray-curable primer composition of the present invention. The blending amount of the above-mentioned solvent can be increased or decreased according to the demand, but the amount of xylene used is 3% by weight or less, preferably 1% by weight or less, preferably not more than 1% by weight relative to the weight of the solid content of the primer coating composition. use. If the amount of xylene used is more than 3% by weight, in addition to stricter environmental restrictions, high temperature and long-term preheating conditions are also required, which is economically disadvantageous.

Although it does not specifically limit as said surface preparation agent, For example, a fluorine type additive, a cellulose type additive, etc. are mentioned. The above-mentioned fluorine-based additive reduces the surface tension and improves the wettability, thereby having an effect of preventing slump when applied to the FRP material. As a specific example of the said fluorine-type additive, MEGAFACE F-558 (made by Dainippon Ink Chemical Co., Ltd.) etc. are mentioned, for example. The above-mentioned cellulose-based additives have a function of imparting film-forming properties at the time of coating.

In the present invention, if the amount of the above-mentioned fluorine-based additive is increased, the adhesion of aluminum vapor deposition or surface coating will be reduced. Since the solid content decreases and the coating film becomes difficult to adhere, it is preferable to use the above-mentioned fluorine additive and the above-mentioned cellulose-based additive in combination.

In the present invention, regarding the addition amount of the above-mentioned surface modifier, the total amount of the above-mentioned fluorine-based additive and the above-mentioned cellulose-based additive with respect to 100 parts by weight of the solid content of the active energy ray-curable primer composition of the present invention is preferably 0.01 to 3.0 parts by mass. When the above-mentioned fluorine-based additive is used alone, it is preferably 0.01 to 1.0 parts by mass, and when the above-mentioned cellulose-based additive is used alone, it is preferably 0.5 to 5.0 parts by mass.

The above-mentioned active energy ray hardening coating composition may further include surface conditioners, ultraviolet absorbers, light stabilizers, antioxidants, storage stabilizers, adhesion imparting agents, organic or inorganic pigments, organic beads, and inorganic beads as required. Generally used additives such as granules and mixtures of these. These additives may be included in ranges of amounts commonly used by those skilled in the art.

The above-mentioned surface conditioner is not particularly limited, and examples include leveling agents for acrylic polymers, anti-slump agents, anti-sag agents such as amide waxes, electrostatic aids for improving leveling of paints, and vapor deposition agents. Metal rust inhibitor, etc. The ultraviolet absorber is not particularly limited, and examples of the ultraviolet absorber include diphenylketone-based, benzotriazole-based, and triazole-based ultraviolet absorbers. It does not specifically limit as a light stabilizer, The light stabilizer, such as a hindered amine type, is mentioned. It does not specifically limit as an antioxidant, A hindered phenol type antioxidant is mentioned. As a storage stabilizer, 4-methoxyphenol, dibutylhydroxytoluene, etc. are mentioned. The adhesion imparting agent is not particularly limited, and examples thereof include benzotriazole-based adhesion imparting agents, silane coupling agents, titanium coupling agents, and the like. It does not specifically limit as an organic or inorganic pigment, A silica, an alumina, carbon black, an aluminum paste, etc. are mentioned. The organic beads, inorganic beads and mixtures thereof are not particularly limited, and examples include silica, alumina, acrylic resin beads, urethane resin beads, and organic beads containing organic pigments or inorganic pigments. Wait.

Coating method When using the primer composition of the present invention to manufacture automobile mirrors, for example, after washing the FRP molded article with a water-based detergent, the primer composition of the present invention is applied to the surface of the molded article. Then, ultraviolet rays are irradiated to form a base coating layer. The above-mentioned coating can be performed by air spray coating, electrostatic coating, dip coating, or the like.

The above-mentioned coating is performed so that the dry film thickness is 8 to 50 µm, and the solvent is evaporated by preheating at 70 to 130° C. for 2 to 25 minutes before the above-mentioned ultraviolet irradiation. If the above-mentioned preheating temperature is lower than 70°C, the solvent will remain in the coating film, resulting in poor water resistance and heat resistance. The appearance is poor, or the photopolymerization initiator is sublimated, and the ultraviolet curability is lowered, and the physical properties of the coating film are lowered. The solvent is evaporated by preheating at 80~120°C, preferably at 90~110°C. If the evaporation time of the above preheating is less than 2 minutes, the solvent will remain in the coating film and the water resistance and heat resistance will be poor. The disadvantage of reducing physical properties. The evaporation time is preferably 2 to 10 minutes, preferably preheating under the conditions of 2 to 5 minutes to evaporate the solvent.

Regarding the above-mentioned ultraviolet irradiation, after the above-mentioned preheating, the primer composition of the present invention can be cured under the condition of a cumulative light amount of 500 to 5000 mJ/cm ² . If the above-mentioned cumulative light amount is less than 500 mJ/cm ² , there is a disadvantage that the physical properties of the coating film are lowered due to insufficient UV curing. If it exceeds 5000mJ/cm ² , there is no effect on the UV curability, but the heat from the UV lamp may cause deformation of the material, thereby deteriorating the appearance. In the above-mentioned ultraviolet irradiation, active energy rays such as high-pressure mercury lamps, metal halide lamps, UV-LED lamps, electron beams, xenon lamps, etc., which are generally used in this field, can be used for the above-mentioned ultraviolet irradiation.

Various layers (eg, metal layers, etc.) can be provided on the primer layer (sometimes also referred to as a "primer layer") formed in the manner described above. As a metal vapor deposition layer, an aluminum vapor deposition layer, an indium vapor deposition layer, a tin vapor deposition layer, etc. are mentioned, for example. The metal vapor deposition layer can be formed by known methods such as vacuum method, sputtering method (eg, DC magnetron sputtering method, RF sputtering method, ion beam sputtering, etc.), electron beam vapor deposition method, and ion plating method. In addition, when the metal vapor deposition layer is an aluminum vapor deposition layer, it can also be formed by coating a coating composition containing a vapor deposited aluminum pigment.

On the said primer layer, a coating layer can also be provided using the well-known coating composition etc. which contain resin components, such as an acrylic resin and a urethane resin, for example. In addition, a coating layer may also be provided on the above-mentioned metal vapor deposition layer as required.

Example The following examples are used to further illustrate the present invention, but the present invention is not limited to them. In the examples, "parts" and "%" are based on quality standards unless otherwise specified.

Polyfunctional (meth)acrylate (A) having two or more (meth)acryloyl groups Hereinafter, the polyfunctional (meth)acrylate (A) which has two or more (meth)acryloyl groups in a molecule|numerator used in an Example is illustrated. Most of them are commercial products, and their specific components are described within the known range. Although there are synthesizers, the synthesis method will be described as Production Example 1 after the illustration. In actual use, these polyfunctional (meth)acrylates can be used alone, or mixed and used by controlling the number of reactive groups. The number of functional groups is described in Table 3 and Table 4.

As for the polyfunctional (meth)acrylate (A) having two or more (meth)acryloyl groups in the molecule, for example, Shin-Nakamura is used as a mixture of dipivalerythritol hexaacrylate and pentaacrylate NK Ester A-DPH, NK Ester A-9500 manufactured by Chemical Co., Ltd., ARONIX M-402 and ARONIX M-403 manufactured by Toagosei, Neomer DA600 manufactured by Sanyo Chemicals; used as a mixture of neopentaerythritol tetraacrylate and triacrylate ARONIX M-450, ARONIX M-303, ARONIX M-305, NK Ester ATMM-3L; ARONIX M-408 was used as a mixture of ditrimethylolpropane tetraacrylate and triacrylate; as trimethyloltriacrylate ARONIX M-309 was used for ester and diacrylate type; NK Ester APG-200 was used as tripropylene glycol diacrylate type; NK Ester A-DCP was used as tricyclodecane dimethanol diacrylate type; For the acrylate system, NK Ester A-NGP was used.

Production Example 1: Production of 1,6-hexamethylene diisocyanate terpolymer and urethane acrylate (b) of hydroxyethyl acrylate 100 parts of butyl acetate and 100 parts of DURANATE TPA-100 (trifunctional isocyanate) manufactured by Asahi Kasei Co., Ltd. were placed in a synthesis vessel equipped with a cooling tube, a stirring device, a dropping device, and a nitrogen introduction tube. In addition, 2-hydroxyethyl acrylate was added in an amount of 1 equivalent of the monomer molecule relative to 1 equivalent of isocyanate group, and 0.1 part of dibutyltin dilaurate was added, and the amount was 0.1% relative to 2-hydroxyethyl acrylate. Dibutylhydroxytoluene was added, stirred and mixed at room temperature, and then reacted for 4 hours while stirring at 80° C. in a nitrogen atmosphere to obtain the target urethane acrylate (b) (number of functional groups: 3) .

Oil modified alkyd resin (B) Hereinafter, production examples of the oil-modified alkyd resin used in the examples will be described. Tables 1-1, 1-2, and Table 2 put together the recipes at the time of production, and the production methods are described in the following production examples. The difference between the manufactured thing used in the Example and the thing used in the comparative example is also described in Table 1 and Table 2. In Table 1 and Table 2, the total components during the reaction, the amount of generated water, the iodine value, oil length (%), hydroxyl value, acid value, weight average molecular weight (Mw) of the obtained oil-modified alkyd resin are also recorded. ), solid content (%), xylene content (%). In addition, in Table 1-1, 1-2 and Table 2, the description below an iodine value is a measured value, and the numerical value other than that shows all weight parts. In addition, in the column under the alkyd number, the difference between the example and the comparative example, and the difference in the case of the comparative example are described very simply.

[Table 1-1]

[Table 1-2]

[Table 2]

Production Example 2: Production method of xylene-rich oil-modified alkyd resin of Patent Document 1 (WO1995/032250) Alkyd-1: Synthesis of pine oil modified alkyd resin with 39% oil length The reaction flask was charged with 2,565 g (8.88 mol) of pine oil fatty acid and 963 g (6.84 mol) of neotaerythritol, and the resulting water was discharged from the system while stirring, and the temperature was raised to 230° C. for 2 hours and 30 minutes. Then, after cooling to 150°C, 582 g (4.13 mol) of neotaerythritol and 506 g (8.16 mol) of ethylene glycol were charged, and 2535 g (17.13 mol) of phthalic anhydride and 148 g of xylene for recycling were added while stirring, and The temperature was raised to 220° C. over 3 hours while discharging the produced water out of the system, and the reaction was carried out until it reached a predetermined acid value. After the completion of the reaction, it was diluted with 5438 g of xylene to obtain a pine oil-modified alkyd resin solution with an acid value of 5, transparency and an oil length of 39%. The iodine value of pine oil fatty acid is 132, the hydroxyl value of the obtained alkyd resin is 150mg/KOH·g, the weight molecular weight is 112,000, the solid content is 53.3%, and the xylene content is 46.7%.

Production Example 3: Production method of oil-modified alkyd resin containing almost no xylene Alkyd-2: Synthesis of pine oil modified alkyd resin with 39% oil length The reaction flask was charged with 2,565 g (8.88 mol) of pine oil fatty acid and 963 g (6.84 mol) of neotaerythritol, and the resulting water was discharged from the system while stirring, and the temperature was raised to 230° C. for 2 hours and 30 minutes. Then, after cooling to 150° C., 582 g (4.13 mol) of neotaerythritol and 506 g (8.16 mol) of ethylene glycol were charged, and 2535 g (17.13 mol) of phthalic anhydride and 148 g of xylene for circulation were added while stirring, Then, the temperature was raised to 220° C. over 3 hours while discharging the produced water out of the system, and the reaction was carried out until it reached a predetermined acid value. After the completion of the reaction, it was diluted with 5438 g of isobutyl acetate to obtain a pine oil-modified alkyd resin solution with an acid value of 4.8, transparency and an oil length of 39%. The hydroxyl value of the obtained alkyd resin was 150 mg/KOH·g, the weight molecular weight was 118,500, the solid content was 53.3%, and the xylene content was 1.2%.

Production Example 4: Production method of oil-modified alkyd resin containing almost no xylene Alkyd-3: Synthesis of pine oil modified alkyd resin with hydroxyl value of 140mg/KOH·g and oil length of 39% In the same manner as in Production Example 2, except that 506 g (8.16 mol) of ethylene glycol in Production Example 2 was changed to 467.2 g (6.85 mol), an acid value of 4.6, a transparent and 39% oil-length modified terpineol was obtained Acid resin solution. The hydroxyl value of the obtained alkyd resin was 140 mg/KOH·g, the weight molecular weight was 108,000, the solid content was 53.1%, and the xylene content was 1.2%.

For alkyd-4, 5, 21 and 22, pine oil modified alkyd resins with target hydroxyl value and oil length of 39% were synthesized by the same method as in Production Example 3 and adjusting the amount of ethylene glycol used.

Alkyd-6~8 were carried out in the same way as alkyd-5 and the reaction end point was adjusted, thereby synthesizing pine oil modified alkyd resin with target acid value and oil length of 39%.

Alkyd-9~12 were carried out in the same way as alkyd-5 and the end point of the reaction was adjusted, thereby synthesizing pine oil modified alkyd resin with target weight molecular weight and oil length of 39%.

Alkyd-13~17 are used to synthesize pine oil modified alkyd resin with target weight molecular weight and oil length by the same method as alkyd-5 except for adjusting the preparation amount of pine oil fatty acid and ethylene glycol.

Alkyd-18~20 were used to synthesize oil-modified alkyd resin with a target oil length of 39% by the same method as alkyd-5 except that pine oil fatty acid was changed into castor oil and safflower oil.

Examples 1 to 47 and Comparative Examples 1 to 16 According to the formulas shown in Tables 3 to 6, the primer coatings of Examples and Comparative Examples were prepared. In Tables 3-1, 3-2 and 4, the formulation ingredients include polyfunctional (meth)acrylate (A), oil-modified alkyd resin (B), photoinitiator (diphenyl ketone or 1- Hydroxycyclohexyl phenyl ketone) and surface conditioner (MEGAFACE F-558), in Tables 5-1, 5-2 and 6, include polyfunctional (meth)acrylate (A), bifunctional monofunctional Body (A), oil modified alkyd resin (B), photoinitiator (diphenyl ketone), surface conditioner (MEGAFACE F-558) and diluent. The amount of xylene contained in the oil-modified alkyd resin (B) is also described in the formulation. MEGAFACE F-558 is a commercially available surface conditioner from DIC Corporation. In Table 6, "alcohol-number" is the alkyd-number, which means the number of the alkyd resin.

Manufacture of FRP automotive mirrors The fiber reinforced plastic (FRP) molded articles for automotive mirrors were washed with isopropyl alcohol (IPA), and after drying, each of the FRP primers obtained in the above Examples and Comparative Examples was applied The composition was air-sprayed on the surface to achieve the predetermined dry film thickness as described in Tables 3-1 to 6. Then, preheat under the predetermined conditions described in Tables 3-1 to 6 to remove the solvent, and then use an 80W/cm ozone type diffusion type high-pressure mercury lamp to irradiate ultraviolet rays with an irradiation amount of 3000mJ/cm ² , thereby curing and curing A base coating layer is formed on the surface of the FRP molded product. Next, after vacuum-evaporating aluminum on the surface of the obtained base coating layer, the top coating material is further air-sprayed thereon to reach a predetermined dry film thickness, and is sintered under predetermined conditions to form a surface coating layer , to produce FRP automotive mirrors.

The obtained FRP-made automotive mirrors were subjected to performance tests for the following items and evaluated. The results are shown in Table 3-1 to Table 6.

[Table 3-1]

[Table 3-2]

[Table 4]

[Table 5-1]

[Table 5-2]

[Table 6]

Performance test evaluation method 1. Appearance of coating film Observe the appearance with the naked eye to check whether there is a smooth surface state, whether there is a rainbow pattern, whitening, cracks, swelling and other defects. Those without defects were evaluated as ◎, those without defects such as rainbow streaks, whitening, cracks, and swelling were evaluated as ○, those with some slight defects were evaluated as △, and those with defects were evaluated as ×.

2. Gloss By visual observation, those with good gloss were evaluated as ⊚, those with sufficient gloss were evaluated as ○, those with part differences were evaluated as Δ, and those with insufficient gloss were evaluated as ×.

3. Adhesion Cut the mirror surface into 100 checkerboards with a width of 2mm with a utility knife, stick transparent adhesive tape on it and peel it off quickly, and count the number of checkerboards that are not peeled off to measure. Those remaining 100/100 were evaluated as ○, those remaining 99/100 to 91/100 were evaluated as Δ, and those remaining 90/100 or less were evaluated as ×.

4. Water resistance It was immersed in a constant temperature water bath at 40° C. for 30 hours, and after being taken out, it was lightly wiped with a cloth, and then the appearance and adhesion were evaluated in the same manner as the above-mentioned method.

5. Moisture resistance It was immersed in a steam bath at 55°C and a humidity of 95% or more for 30 hours, and after taking it out, it was wiped lightly with a cloth, and then the appearance and adhesion were evaluated in the same manner as the above-mentioned method.

6. Heat resistance It was left to stand in a hot air circulating drying oven at 150° C. for 24 hours, and after being taken out, it was left to cool to room temperature, and then the appearance and adhesion were evaluated in the same manner as the above-mentioned method.

7. Temperature and humidity cycle resistance Appearance and adhesion were evaluated according to the temperature and humidity cycle test (JIS C 60068-2-38). Appearance and adhesion were evaluated as good up to 10 cycles as ⊚, good up to 5 cycles as ◯, good up to 3 cycles as Δ, and 3 cycles or less as ×.

8. Term of use Store at 40°C for 3 months and observe the storage stability. Those with no significant change in viscosity and no gel formation were evaluated as ○, and those with significant viscosity change or gel formation were evaluated as ×.

Reading Tables 3-1 to 6, it can be seen that the examples all show ideal results in the performance test. In Comparative Examples 1 to 5, the oil-modified alkyd resins of the examples of the old Japanese patent (cited document 1) were used, and the blending amount of xylene was high. Comparative Examples 6 to 10 use alkyd resin-5, Comparative Examples 6 and 7 are oil-modified alkyd resins (B) whose blending amounts are out of the scope of the claims, and Comparative Example 8 uses monofunctional monomers , Comparative Examples 9 to 16 are those whose hydroxyl value or acid value of the oil-modified alkyd resin (B) falls outside the scope of claim 1.

(none)

Claims (6)

An active energy ray hardening primer coating composition for FRP used for metal evaporation, comprising a polyfunctional (meth)acrylate (A) and an oil-modified alkyd resin (B); The polyfunctional (meth)acrylate (A) has two or more (meth)acryloyl groups in the molecule, and is modified with respect to the polyfunctional (meth)acrylate (A) and the oil-modified alkyd The total amount of resin (B) is 100 parts by mass, and the polyfunctional (meth)acrylate (A) is contained in an amount of 55 to 85 parts by mass; and, The oil-modified alkyd resin (B) is contained in an amount of 15 to 45 parts by mass relative to 100 parts by mass of the total amount of the polyfunctional (meth)acrylate (A) and the oil-modified alkyd resin (B). ), and the aforementioned oil-modified alkyd resin (B) has an oil length of 35 to 50%, an acid value of 0.01 to 10 mgKOH/g, a hydroxyl value of 80 to 130 mgKOH/g, and a weight average molecular weight of 80,000 to 150,000. The active energy ray-curable primer coating composition for FRP for metal vapor deposition according to claim 1, wherein the oil-modified alkyd resin (B) is modified by the following oils and fats: At least one of the group consisting of pine oil, soybean oil, safflower oil, linseed oil, tung oil, castor oil and mixtures of these oils. The active energy ray-curable primer coating composition for FRP for metal vapor deposition according to claim 1 or 2, wherein the oil and fat component (b) used to modify the oil-modified alkyd resin (B) ) are those with an iodine value of 80 to 160 alone or after mixing two or more types of oils and fats. The active energy ray-curable primer coating composition for FRP for metal vapor deposition according to any one of claims 1 to 3, wherein the active energy ray-curable primer coating composition is further relative to the aforementioned components ( The total amount of A) and (B) is 100 parts by mass, and the photopolymerization initiator (C) is blended in an amount of 1 to 15 parts by mass. The active energy ray-curable primer coating composition for FRP for metal vapor deposition according to any one of claims 1 to 4, wherein the active energy ray-curable primer coating composition further comprises: selected from the group consisting of: At least one selected from the group consisting of surface conditioners, ultraviolet absorbers, light stabilizers, antioxidants, storage stabilizers, adhesion imparting agents, and mixtures thereof. The active energy ray-curable primer coating composition for FRP for metal vapor deposition according to any one of claims 1 to 5, wherein the active energy ray-curable primer coating composition further comprises: selected from the group consisting of: At least one of the group consisting of organic pigments, inorganic pigments, organic beads, inorganic beads and mixtures thereof.