WO2021210467A1 - Composition de résine photodurcissable, matériau de revêtement pour véhicule et article revêtu - Google Patents

Composition de résine photodurcissable, matériau de revêtement pour véhicule et article revêtu Download PDF

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Publication number
WO2021210467A1
WO2021210467A1 PCT/JP2021/014787 JP2021014787W WO2021210467A1 WO 2021210467 A1 WO2021210467 A1 WO 2021210467A1 JP 2021014787 W JP2021014787 W JP 2021014787W WO 2021210467 A1 WO2021210467 A1 WO 2021210467A1
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Prior art keywords
acrylic resin
hydroxyl group
resin composition
photocurable
containing acrylic
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PCT/JP2021/014787
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English (en)
Japanese (ja)
Inventor
英明 奥田
大嗣 馬野
優吾 竹本
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日本ペイント・オートモーティブコーティングス株式会社
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Priority to JP2021519683A priority Critical patent/JP6940720B1/ja
Publication of WO2021210467A1 publication Critical patent/WO2021210467A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to photocurable resin compositions, vehicle paints, and painted articles.
  • the convex part When painting a material with uneven surface, the convex part should be thickened to hide it, or it should be polished with sandpaper to make it smooth before painting, and the concave part should be pinned with a putty or the like. Measures such as filling holes and painting putty to smooth the surface have been taken. However, such pretreatment not only reduces productivity, but also has problems such as an increase in volatile organic compounds (hereinafter referred to as VOC) due to an increase in the amount of paint used. Also, if the cause of the recess is a pinhole generated by the air contained in the material, it is difficult to completely fill all the pinholes with putty before painting, and air remains in the pinholes. There was a case. If painting and baking are performed with air remaining in the pinhole, the liquid paint after painting will be sucked into the pinhole, or the air inside the pinhole will expand during baking and the paint film will be damaged. There was a problem that defects would occur.
  • VOC volatile organic compounds
  • Fiber reinforced plastic material (hereinafter referred to as FRP material) is lightweight while having excellent properties such as strength, rigidity, and dimensional stability compared to iron and aluminum.
  • FRP material Fiber reinforced plastic material
  • the FRP material is a material that is prone to unevenness because it is molded by kneading a plurality of materials.
  • the unevenness referred to here is a segregated unevenness formed by the fibers appearing on the surface of the material due to insufficient mixing of the fibers, a convex due to the popping out of a single fiber, and a pin that is concave due to the appearance of air bubbles mixed when mixing the fibers on the surface.
  • the FRP material is a material in which coating defects are likely to occur, so that the productivity is poor, and the FRP material has been applied only to some parts such as those for luxury cars and competitions. Therefore, in order to increase the number of members using FRP material having excellent characteristics, it has been required to develop a putty paint having an excellent sealing effect and excellent suppression of coating defects.
  • Patent Document 1 contains (a) a mixed polyol of an acrylic polyol having a hydroxyl value of 15 to 25 and an acrylic polyol having a hydroxyl value of 35 to 45, and (b) a mixture of xylylene diisocyanate-based polyisocyanates having different isocyanate group contents.
  • a coating method is disclosed in which a two-component urethane coating material is brought into contact with an atmosphere containing a tertiary amine vapor and cured.
  • such a coating method is inconvenient in terms of safety, environmental load, and cost, such as large-scale equipment for contacting with dangerous tertiary amine vapor and wastewater treatment, in addition to the conventional baking process. there were.
  • Patent Document 2 describes a photocurable component (A) containing a urethane (meth) acrylate having 6 or more (meth) acryloyl groups, a hydroxyl group-containing acrylic resin (B) having a hydroxyl value of 10 to 200 mgKOH / g, and a polyisocyanate (C). ) Is disclosed. However, this photocurable resin composition has not been studied as a putty for suppressing coating defects. Further, the hydroxyl group-containing acrylic resin (B) was not finely limited.
  • the present invention relates to a photocurable resin composition having an excellent sealing effect. Further, when the above-mentioned photocurable resin composition is used as a putty, it is possible to suppress coating defects of topcoat coating materials such as colored coating materials and clear coating materials and improve the coating appearance. Further, since it has excellent adhesion to the topcoat paint, it is possible to obtain a multi-layer coating film having excellent strength and durability.
  • the present invention is a photocurable component (A), which is a polyfunctional acrylate having 4 or more (meth) acrylate groups.
  • a hydroxyl group-containing acrylic resin (B-1) having a weight average molecular weight in the range of 3000 to 8000, It contains a hydroxyl group-containing acrylic resin (B-2), a particle component (C), and a polyisocyanate (D) having a weight average molecular weight in the range of 10,000 to 30,000.
  • the compounding ratio of the polyisocyanate (D) is 10 to 100% by mass with respect to 100% by mass of the total amount of the photocurable component (A), the acrylic resin (B-1), the acrylic resin (B-2) and the particle component (C).
  • the present invention relates to a photocurable resin composition characterized by being%.
  • the acrylic resin (B-1) preferably has a hydroxyl value in the range of 120 to 200 mgKOH / g.
  • the acrylic resin (B-2) preferably has a hydroxyl value in the range of 5 to 70 mgKOH / g.
  • the present invention relates to a vehicle coating material comprising the above-mentioned photocurable resin composition.
  • the present invention also relates to a coated article having a cured coating film obtained by combining the above-mentioned photocurable resin composition with UV curing and thermosetting.
  • the photocurable resin composition of the present invention has an excellent sealing effect, it is possible to hide the unevenness on the surface of the object to be coated. Further, it is possible to obtain the effect of suppressing subsequent coating defects.
  • the present invention comprises a photocurable component (A) which is a polyfunctional acrylate having 4 or more (meth) acrylate groups, a hydroxyl group-containing acrylic resin (B-1) having a weight average molecular weight in the range of 3000 to 8000.
  • the photocurable resin composition of the present invention is used by directly coating it on a resin base material having many surface irregularities such as FRP. It may be used on a polished substrate.
  • the photocurable resin composition contains a high molecular weight hydroxyl group-containing acrylic resin (B-2) and a particle component (C), the fluidity of the liquid paint is controlled after painting, and the base material is used. It is possible to reduce the occurrence of concave defects generated by flowing into the segregated concaves and pinholes above. Further, the high molecular weight hydroxyl group-containing acrylic resin (B-2) is designed to have a low hydroxyl value to reduce the influence of shrinkage due to thermal curing with the polyisocyanate (D), thereby improving dimensional stability. It is also possible to improve the adhesion with the base material and the topcoat paint.
  • the photocurable resin composition contains a photocurable component (A) and a hydroxyl group-containing acrylic resin (B-1) having a low molecular weight, a coating film having a higher surface crosslink density than UV curing can be obtained. Since it can be formed and heat-cured to form a coating film with a high crosslink density inside the coating film, the air inside the pinholes expands in the process after applying the topcoat paint, causing damage to the coating film. Painting defects can be reduced. Further, since the photocurable resin composition contains the photocurable component (A) and the hydroxyl group-containing acrylic resin (B-1) having a low molecular weight, the coating film thickness can be increased by concealing the convex portions.
  • the photocurable resin composition of the present invention contains a high molecular weight hydroxyl group-containing acrylic resin (B-2) and a particle component (C), so that the viscosity immediately after painting is controlled and the smoothness is not sucked into the recess.
  • High coating film can be obtained.
  • a coating film having good adhesion to the base material and the top coat can be obtained by a thermal reaction with the polyisocyanate (D).
  • a coating film having a high crosslink density can be obtained even at various film thicknesses.
  • the convex portion can be concealed, the expansion of the air remaining in the uneven portion can be suppressed, and the smooth state of the comprehensive coating film coated with the topcoat paint can be maintained. Therefore, the photocurable resin composition of the present invention is suitably used for an object to be coated having irregularities, and particularly has excellent performance as a putty.
  • the present invention will be described in detail.
  • the photocurable resin composition of the present invention contains a polyfunctional acrylate having 4 or more (meth) acrylate groups as the photocurable component (A).
  • the polyfunctional (meth) acrylate having 4 or more (meth) acrylate groups described above has good polymerization activity when irradiated with active energy rays.
  • the photocurable resin composition contains a polyfunctional (meth) acrylate having 4 or more (meth) acrylate groups, there is an advantage that a coating film having a high crosslink density can be obtained on the surface. ..
  • the polyfunctional (meth) acrylate can be prepared by dealcoholizing the polyhydric alcohol and the (meth) acrylate.
  • Specific examples of the polyfunctional (meth) acrylate include 4 such as pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, and trimethylolpropane tetra (meth) acrylate.
  • Functional (meth) acrylate Five-functional (meth) acrylates such as dipentaerythritol penta (meth) acrylate and tripentaerythritol penta (meth) acrylate; Hexa-functional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate and tripentaerythritol hexa (meth) acrylate; 7-functional or higher (meth) acrylates such as tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate; And so on.
  • the polyfunctional (meth) acrylate used in the present invention is not particularly limited in molecular weight, but is preferably having a molecular weight of 3000 or less. That is, it is preferable that the compound does not correspond to a polymer but has a relatively low molecular weight. Such a molecular weight is a value calculated from the chemical structural formula of the polyfunctional (meth) acrylate.
  • One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be mixed and used.
  • the photocurable resin composition of the present invention may be a combination of other photocurable compounds.
  • the blending ratio of the photocurable component (A) contained in the photocurable resin composition is the photocurable component (A), the hydroxyl group-containing acrylic resin (B-1), the hydroxyl group-containing acrylic resin (B-2) and the particles. It is preferably 6% by mass or more and 54% by mass or less, and more preferably 20% by mass or more and 40% by mass or less, based on 100% by mass of the total amount of the component (C).
  • the blending ratio of the photocurable component (A) is 6% by mass or more, the crosslink density on the surface of the obtained coating film can be improved. Further, when it is 54% by mass or less, there is an advantage that the adhesion between the base material and the topcoat paint can be kept good by reducing excessive curing shrinkage.
  • the hydroxyl group-containing acrylic resin (B-1) is a low molecular weight hydroxyl group-containing acrylic resin having a weight average molecular weight in the range of 3000 to 8000.
  • the weight average molecular weight is in the range of 3000 to 8000, the hydroxyl group-containing acrylic resin (B-1) is crosslinked and a cured coating film having a high crosslink density is formed when the coating is applied on the coating and the heat is cured. can do.
  • the weight average molecular weight is preferably 4000 or more, and more preferably 6000 or more.
  • the weight average molecular weight in the present specification is a value measured by gel permeation chromatography using HLC-8200 manufactured by Tosoh Corporation.
  • the measurement conditions are as follows. Column TSgel Super Multipore HZ-M 3 development solvent Tetrahydrofuran Column inlet oven 40 ° C. Flow rate 0.35 ml Detector RI Standard polystyrene PS oligomer kit manufactured by Tosoh Corporation
  • the "acrylic resin” refers to a polymer obtained by polymerizing a monomer composition containing at least one monomer of acrylic acid and its ester, methacrylic acid and its ester.
  • a suitable monomer composition capable of forming the hydroxyl group-containing acrylic resin (B-1) according to the present invention and satisfying the above conditions includes, for example, a hydroxyl group such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate.
  • Acrylic acid hydroxy ester contains at least one of a hydroxyl group-containing methacrylic acid hydroxy ester such as 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate; and, if necessary, acrylic acid; Acrylic acid esters such as methyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isobolonyl acrylate; methacrylic acid; methyl methacrylate, butyl methacrylate, methacrylic acid.
  • a hydroxyl group-containing methacrylic acid hydroxy ester such as 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate
  • Acrylic acid esters such as methyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acryl
  • the composition of the monomer composition may be appropriately adjusted according to various physical properties required for the hydroxyl group-containing acrylic resin (B-1).
  • the monomer composition can be polymerized using a solvent such as butyl acetate. Further, the polymerization conditions such as the type of the solvent, the concentration of the monomer composition at the time of polymerization, the type and amount of the polymerization initiator, the polymerization temperature, the polymerization time, etc., have various physical properties required for the hydroxyl group-containing acrylic resin (B-1). It can be adjusted as appropriate. Therefore, the method for producing the hydroxyl group-containing acrylic resin (B-1) is not particularly limited, and a commercially available hydroxyl group-containing acrylic resin (B-1) may be used.
  • the hydroxyl group-containing acrylic resin (B-1) preferably has a hydroxyl value (OHV) in the range of 120 to 200 mgKOH / g.
  • OCV hydroxyl value
  • the lower limit of the hydroxyl value is more preferably 150 mgKOH / g.
  • the upper limit of the hydroxyl value is more preferably 170 mgKOH / g.
  • the hydroxyl value can be determined by the neutralization titration method using the potassium hydroxide aqueous solution described in JIS K 0070.
  • the compounding ratio of the hydroxyl group-containing acrylic resin (B-1) is a total amount of 100 mass of the photocurable component (A), the hydroxyl group-containing acrylic resin (B-1), the hydroxyl group-containing acrylic resin (B-2) and the particle component (C). It is preferably 4% by mass or more and 36% by mass or less, and more preferably 10% by mass or more and 30% by mass or less.
  • the glass transition temperature of the hydroxyl group-containing acrylic resin (B-1) is preferably ⁇ 15 ° C. or higher and 45 ° C. or lower, and more preferably 0 ° C. or higher and 30 ° C. or lower. When the glass transition temperature is within such a range, the coating film can have high crosslink density and elasticity.
  • a value measured by the following steps with a differential scanning calorimeter (DSC) thermal analyzer SSC5200 (manufactured by Seiko Electronics Co., Ltd.) was used. Specifically, a step of raising the temperature from 20 ° C. to 150 ° C.
  • step 3 the value obtained from the chart at the time of raising the temperature in step 3 was defined as the glass transition temperature. That is, the temperature indicated by the arrow in the chart shown in FIG. 1 was defined as Tg (glass transition temperature).
  • the solid acid value (AV) of the hydroxyl group-containing acrylic resin (B-1) is preferably 0.5 mgKOH / g or more and 15 mgKOH / g or less, and more preferably 2 mgKOH / g or more and 10 mgKOH / g or less. ..
  • the acid value of the hydroxyl group-containing acrylic resin (B-1) is within such a range, the adhesion to the base material and the topcoat paint can be improved.
  • the hydroxyl group-containing acrylic resin (B-2) is a high molecular weight hydroxyl group-containing acrylic resin having a weight average molecular weight in the range of 10,000 to 30,000.
  • the weight average molecular weight is preferably 13000 or more, and preferably 23000 or less.
  • the above-mentioned hydroxyl group-containing acrylic resin (B-2) can be formed, and the suitable monomer composition satisfying the above-mentioned conditions is not particularly limited, and the one described in the above-mentioned hydroxyl group-containing acrylic resin (B-1) can be used.
  • the hydroxyl group-containing acrylic resin (B-2) preferably has a hydroxyl value (OHV) in the range of 5 to 70 mgKOH / g.
  • OCV hydroxyl value
  • the hydroxyl value is more preferably 20 to 55 mgKOH / g.
  • the glass transition temperature of the hydroxyl group-containing acrylic resin (B-2) is preferably 40 ° C. or higher and 100 ° C. or lower, and more preferably 50 ° C. or higher and 80 ° C. or lower. When the glass transition temperature is within such a range, the coating film can have excellent adhesion to the substrate in particular.
  • the solid acid value (AV) of the hydroxyl group-containing acrylic resin (B-2) is preferably 0.5 mgKOH / g or more and 30 mgKOH / g or less, and more preferably 2 mgKOH / g or more and 10 mgKOH / g or less. ..
  • the coating film can obtain particularly excellent adhesion to the substrate.
  • the compounding ratio of the hydroxyl group-containing acrylic resin (B-2) is a total amount of 100 mass of the photocurable component (A), the hydroxyl group-containing acrylic resin (B-1), the hydroxyl group-containing acrylic resin (B-2) and the particle component (C). It is preferably 4% by mass or more and 36% by mass or less, and more preferably 10% by mass or more and 30% by mass or less.
  • the SP values of the hydroxyl group-containing acrylic resins (B-1) and (B-2) are not particularly limited, but the difference is preferably less than 1.
  • the difference in SP value is less than 1, the compatibility of the hydroxyl group-containing acrylic resins (B-1) and (B-2) is high, so that a highly uniform coating film can be formed, thereby providing excellent physical properties. It is preferable in that a coating film having a coating film can be formed.
  • the difference between the SP values is more preferably less than 0.5.
  • the SP value means the SP value by the turbidity method.
  • the SP value is an abbreviation for solubility parameter and is a measure of solubility. The larger the SP value, the higher the polarity, and conversely, the smaller the value, the lower the polarity.
  • the photocurable resin composition of the present invention further contains a particle component (C).
  • a particle component (C) By containing the particle component (C), the viscosity of the coating material can be controlled, and a film can be formed with a sufficient thickness for concealing unevenness. In addition, it becomes difficult for the liquid coating composition to enter the recesses and pinholes on the surface of the object to be coated immediately after coating, and a good sealing effect can be obtained.
  • the particle component (C) is not particularly limited as long as it is usually blended in the resin composition, but the average particle size is preferably 20 ⁇ m or less. When the average particle size is 20 ⁇ m or less, a better sealing effect can be expected. The average particle size is more preferably 10 ⁇ m or less. The average particle size represents D50 measured using a laser diffraction type particle size distribution measuring device.
  • the particle component (C) may be an inorganic substance particle or an organic polymer particle.
  • the inorganic substance particles include natural or synthetic mica, barium sulfate, aluminum powder, aluminum flakes, iron oxide, kaolin clay, talc, silica fine powder, titanium oxide and the like.
  • the silica fine powder include wet silica, dry silica, colloidal silica and the like.
  • organic polymer particles examples include fluororesins such as polytetrafluoroethylene, polyethylene, polypropylene, silicones, celluloses, urethanes, nylons, polyesters, phenol resins, acrylic resins, amino resins, polyamide resins and modified resins thereof. Can be mentioned.
  • fluororesins such as polytetrafluoroethylene, polyethylene, polypropylene, silicones, celluloses, urethanes, nylons, polyesters, phenol resins, acrylic resins, amino resins, polyamide resins and modified resins thereof. Can be mentioned.
  • the particle component (C) is preferably at least one selected from talc, silica, and kaolin clay. Moreover, you may use 2 or more types together.
  • the blending ratio of the particle component (C) is 100% by mass of the total amount of the photocurable component (A), the hydroxyl group-containing acrylic resin (B-1), the hydroxyl group-containing acrylic resin (B-2) and the particle component (C). , 6% by mass or more and 54% by mass or less, and more preferably 25% by mass or more and 45% by mass or less. If the blending ratio is less than 6% by mass, the fluidity of the coating liquid becomes high and may flow into the pinholes to impair the smoothness of the coating film surface. On the other hand, if an amount exceeding 54% by mass is blended, the fluidity is lowered, the smoothness of the coating film surface is impaired, and the hue and smoothness of the topcoat coating material may be lowered.
  • the photocurable resin composition of the present invention further contains polyisocyanate (D).
  • polyisocyanate (D) By blending the polyisocyanate (D), a crosslinked structure is formed with the hydroxyl group-containing acrylic resins (B-1) and (B-2) when the coating film formed above is thermoset, and the coating film is formed.
  • the strength can be increased and coating defects can be suppressed.
  • the adhesion to the coating film layer formed on the top can be enhanced, and the strength as a multi-layer coating film can be enhanced.
  • the blending ratio of the polyisocyanate (D) is 100% by mass based on the total amount of the photocurable component (A), the hydroxyl group-containing acrylic resin (B-1), the hydroxyl group-containing acrylic resin (B-2) and the particle component (C). It is 10 to 100% by mass. If the blending ratio is less than 10% by mass, the crosslink density of the coating film becomes low, the coating film cannot follow the expansion of the air contained in the pinholes, and the appearance of the topcoat paint may be deteriorated. On the other hand, when an amount exceeding 100% by mass is blended, the total amount of the hydroxyl group-containing acrylic resin (B-2) and the particle component (C) becomes low, so that the fluidity of the coating film becomes high and flows into the pinhole. The smoothness of the coating film surface may be impaired.
  • the polyisocyanate (D) is not particularly limited as long as it is a compound having two or more isocyanate groups, and for example, aromatics such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate.
  • aromatics such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate.
  • Group Aliphatic such as hexamethylene diisocyanate
  • Alicyclic such as isophorone diisocyanate
  • Monomer thereof and multimers such as bullet type, nurate type, adduct type and the like.
  • D polyisocyanate
  • Duranate 24A-90PX NCO: 23.6%, trade name, manufactured by Asahi Kasei Corporation
  • Sumijour N-3200-90M trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.
  • Takenate D165N-90X (trade name, manufactured by Mitsui Chemicals, Inc.)
  • Sumijour N-3300 Sumijour N-3500 (trade name, manufactured by Sumitomo Bayer Urethane)
  • Duranate THA-100 trade name, manufactured by Asahi Kasei).
  • blocked isocyanates in which these are blocked can also be used.
  • the photocurable resin composition may further contain ordinary additives used in paints.
  • ordinary additives include coloring pigments, moisture-resistant pigments, other resins, dispersants, anti-settling agents, organic solvents, antifoaming agents, thickeners, rust inhibitors, ultraviolet absorbers, antioxidants, hindered amines, etc.
  • Known additives such as surface conditioners can be mentioned.
  • the photocurable resin composition of the present invention is preferably adjusted in viscosity so as to exert a high sealing effect, and the tinx value of the paint to be coated is preferably 3 or more and 9 or less. If the tinx value of the paint is less than 3, the fluidity of the paint is high and it may flow into the pinholes to impair the smoothness of the paint film surface. If the chixo value of the paint exceeds 9, the fluidity of the paint is low and the surface of the paint after painting is not smoothed, so that the smoothness, hue and appearance of the topcoat paint are impaired.
  • the chixo values in the present specification are values measured using a TVB-22L BL type viscometer manufactured by Toyo Seiki Co., Ltd.
  • the measuring method and the calculation method of the chixo value are as follows: the paint is adjusted to a liquid temperature of 20 ° C., a measuring rotor is attached to a BL type viscometer, and the rotor rotation speeds of 60 rotations / minute and 6 rotations / minute are measured.
  • the photocurable resin composition of the present invention can be particularly suitably used as a putty made of a material having irregularities on its surface.
  • the use as a putty will be described in detail below.
  • the material having irregularities on the surface is not particularly limited, and examples thereof include FRP materials in which fibers such as glass, carbon, Kevlar, high molecular weight polyethylene, boron, and zylon are composited. Further, even a resin having a high water absorption rate can prevent defects due to water evaporation during thermosetting, so that it can be applied to materials such as nylon, ABS, ASA, PET, PBT-PET, PMMA, and polycarbonate. can.
  • the photocurable resin composition of the present invention is suitable as a vehicle paint.
  • Such a vehicle paint is also one of the present inventions.
  • the method for coating the photocurable resin composition of the present invention is not particularly limited. For example, after cleaning the FRP molded product with an aqueous cleaning agent, the above photocurable resin composition is coated on the surface of the molded product, and then. A coating film can be formed by irradiating with ultraviolet rays. Further, after painting, in order to remove the solvent remaining in the paint, air drying may be performed before UV irradiation or a solvent removing step may be added to shorten the process.
  • the above coating is not particularly limited, and can be performed by a known method such as air spray coating, electrostatic coating, or immersion coating.
  • the coating is performed so that the dry film thickness is 10 to 70 ⁇ m, and air-dried or preheated at room temperature to 100 ° C. for 5 to 25 minutes, preferably 5 to 20 minutes before the irradiation with ultraviolet rays. It is preferable to evaporate the solvent. If the temperature of the preheat exceeds 100 ° C., the performance is not affected, but it is economically disadvantageous.
  • the ultraviolet irradiation is preferably performed under the condition of about 500 to 5000 mJ / cm 2.
  • the photocurable resin composition of the present invention can be cured by the above-mentioned ultraviolet irradiation.
  • active energy rays such as high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LED lamps, and electron beams, which are usually used in the art, can be used.
  • active energy rays such as high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LED lamps, and electron beams, which are usually used in the art, can be used.
  • a coated article having a cured coating film obtained by curing the photocurable resin composition of the present invention is also one of the present inventions.
  • a top coat such as a base paint and a clear paint.
  • a second primer coating may be applied, if necessary, before the coating of the top coating paint.
  • the second primer coating is not particularly limited, and for example, a known plastic primer may be applied.
  • the photocurable resin composition of the present invention it is preferable that after coating, UV irradiation is performed to cure the surface, and then base coating, clear coating and, if necessary, a second putty coating are performed.
  • the heat curing may be performed for each coating of the second putty paint, the base paint, and the clear paint, or may be performed after the second putty paint, the base paint, and the clear paint are applied from the viewpoint of productivity.
  • the putty paint may be heat-cured.
  • the base coating and the clear coating are not particularly limited, and for example, the clear coating can be applied to a known solvent-based base coating or water-based base coating and heat-cured.
  • the method for applying the topcoat coating composition is not particularly limited, and for example, air spray coating, airless spray coating, bell coating, or the like can be adopted.
  • the baking temperature of the topcoat coating composition is preferably, for example, 70 to 130 ° C. in view of the balance between rapid curing and prevention of deformation of the FRP molded product. More preferably, it is 80 to 120 ° C.
  • the baking time is usually 10 to 60 minutes, preferably 15 to 50 minutes, and more preferably 20 to 40 minutes. If the baking time is less than 10 minutes, the coating film is not sufficiently cured, and the performance such as water resistance and solvent resistance of the cured coating film is deteriorated. On the other hand, if the baking time exceeds 60 minutes, it is over-cured and the adhesion in recoating is lowered, the total time of the painting process is lengthened, and the energy cost is increased.
  • this baking time means the time that the surface of the base material actually keeps the target baking temperature, and more specifically, the time until the target baking temperature is reached is not considered, and the target It means the time when the temperature is reached and the temperature is maintained.
  • Examples of the heating device used for simultaneously baking the uncured film of the paint include a drying furnace using a heating source such as hot air, electricity, gas, or infrared rays, and two or more of these heating sources are used in combination. It is preferable to use a drying oven because the drying time is shortened.
  • the photocurable resin composition of the present invention can be particularly preferably used as a paint for vehicles.
  • vehicle include automobile bodies made of FRP, various automobile parts such as spoilers, and the like.
  • Table 1 shows the same equipment as that used for the synthesis of the hydroxyl group-containing acrylic resin 1- (1).
  • the physical characteristics are also shown in Table 1.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and is a polystyrene-equivalent weight average molecular weight.
  • Solubility parameter (SP value) The solubility parameter (SP value) was actually measured by the method described herein.
  • Glass transition temperature (Tg) The glass transition temperature (Tg) was measured using a DSC (Differential Scanning Calorimetry) manufactured by Seiko Electronics Inc.
  • St Styrene EHMA: 2-Ethylhexyl methacrylate HEMA: 2-Hydroxyethyl methacrylate MAA: Methacrylic acid polymerization initiator: Kayaester-O (hydrogen peroxide-based polymerization initiator manufactured by Kayaku Akzo Corporation)
  • Table 2 shows the same equipment as that used for the synthesis of the hydroxyl group-containing acrylic resin 1- (1).
  • Table 2 shows the same synthesis procedure and operation as those for the synthesis of the hydroxyl group-containing acrylic resin 1- (1) except that the solvent, monomer, initiator, and polymerization temperature were changed so as to obtain the stated blending amount.
  • a hydroxyl group-containing acrylic resin 2- (1) to 2- (9) was obtained.
  • the physical characteristics are also shown in Table 2.
  • Photo-curing component (A) The photocurable component (A) used is as follows. Pentaerythritol tetraacrylate (manufactured by Sartmer: SR295) Ditrimethylolpropane tetraacrylate (manufactured by Sartmer: SR355) Dipentaerythritol pentaacrylate (manufactured by Sartmer: SR399) Dipentaerythritol hexaacrylate (manufactured by Sartmer: DPHA)
  • Particle component (C) The particle component (C) used is as follows.
  • Polyisocyanate (D) The polyisocyanate (D) used is as follows.
  • TPA-100 Isocyanurate type
  • Hexamethylene isocyanurate 24A-100 Burette type
  • Hexamethylene diisocyanate P301-75E Adduct type
  • Asahi Kasei Corporation Hexamethylene isocyanurate manufactured by Asahi Kasei Corporation
  • the obtained photopolymerizable resin composition was spray-coated so that the dry film thickness was 35 ⁇ m, and heated in a hot air drying oven at 80 ° C. for 5 minutes to remove the solvent.
  • ECS-4011GX manufactured by Eye Graphics Co., Ltd.
  • ultraviolet rays having an integrated light intensity of 2000 mJ / cm 2 were irradiated to obtain a cured coating film.
  • the amount of light in the ultraviolet irradiation was measured using an eye ultraviolet integrated illuminance meter UV METER UVPF-A1 (light receiving unit 365 nm) manufactured by Eye Graphics.
  • Example 2-35, Comparative Examples 1-10 The coating films of Examples 2 to 35 and Comparative Examples 1 to 10 were formed in the same manner as in Example 1 except that the formulations were changed to those shown in Tables 4 to 9, and final coated plates were obtained.
  • a laminated film was formed by the following method.
  • the solvent-based base paint composition manufactured by Nippon Paint Automotive Coatings Co., Ltd .: R-160
  • a clear coating composition manufactured by Nippon Paint Automotive Coatings Co., Ltd .: R-2830 was applied so that the film thickness of the dry coating film was 25 ⁇ m.
  • the mixture was allowed to stand for 10 minutes and then heat-cured at 80 ° C. for 30 minutes to obtain a test piece having a multi-layer coating film.
  • the photocurable resin composition of the present invention can obtain coatability and good coating film physical properties.
  • the photocurable resin composition of the present invention can be suitably used as a resin composition to be directly coated on a resin member having irregularities on the surface.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de résine photodurcissable qui présente un excellent effet de remplissage et qui permet de dissimuler toute irrégularité de la surface d'un objet à revêtir. La composition de résine photodurcissable est caractérisée en ce qu'elle comprend : un constituant photodurcissable (A) qui consiste en un acrylate polyfonctionnel comprenant au moins quatre groupes (méth)acrylate; une résine acrylique contenant un groupe hydroxyle (B-1) ayant une masse moléculaire moyenne en poids dans la plage de 3 000 à 8 000; une résine acrylique contenant un groupe hydroxyle (B-2) ayant une masse moléculaire moyenne en poids dans la plage de 10 000 à 30 000; un constituant particulaire (C); et un polyisocyanate (D), le rapport de mélange du polyisocyanate (D) étant de 10 à 100 % en masse par rapport aux 100 % en masse de la quantité totale du constituant photodurcissable (A), de la résine acrylique (B-1), de la résine acrylique (B-2) et du constituant particulaire (C).
PCT/JP2021/014787 2020-04-14 2021-04-07 Composition de résine photodurcissable, matériau de revêtement pour véhicule et article revêtu WO2021210467A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0271876A (ja) * 1988-09-05 1990-03-12 Kansai Paint Co Ltd Ｆｒｐ成形品の塗装方法
JP2000297112A (ja) * 1999-04-15 2000-10-24 Hitachi Chem Co Ltd 光硬化性樹脂組成物、塗料及び硬化塗膜の製造法
WO2016020978A1 (fr) * 2014-08-05 2016-02-11 オリジン電気株式会社 Composition de revêtement durcissable à la chaleur et à la lumière et procédé de formation de film de revêtement, procédé de transfert sous pression de l'eau
JP2016512273A (ja) * 2013-03-15 2016-04-25 エルジー・ケム・リミテッド プラスチックフィルム
WO2018155548A1 (fr) * 2017-02-22 2018-08-30 パナック株式会社 Composition de résine et film de revêtement dur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0271876A (ja) * 1988-09-05 1990-03-12 Kansai Paint Co Ltd Ｆｒｐ成形品の塗装方法
JP2000297112A (ja) * 1999-04-15 2000-10-24 Hitachi Chem Co Ltd 光硬化性樹脂組成物、塗料及び硬化塗膜の製造法
JP2016512273A (ja) * 2013-03-15 2016-04-25 エルジー・ケム・リミテッド プラスチックフィルム
WO2016020978A1 (fr) * 2014-08-05 2016-02-11 オリジン電気株式会社 Composition de revêtement durcissable à la chaleur et à la lumière et procédé de formation de film de revêtement, procédé de transfert sous pression de l'eau
WO2018155548A1 (fr) * 2017-02-22 2018-08-30 パナック株式会社 Composition de résine et film de revêtement dur

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