JP2002508012A - Matte paste for cationic paint system - Google Patents

Abstract

  (57) [Summary] The use of 10-40% by weight of diluents such as vinyl ethers (e.g., CHVE, DVE3) and acrylates (HDDA, TPGDA, DPGDA) with the cycloaliphatic epoxy resin greatly enhances the action of the porous silica and provides other desirable properties. It is possible to produce matte and semi-gloss coatings based on cationic or hybrid curing (cationic / free radical curing) without adversely affecting the coating properties.

Description

DETAILED DESCRIPTION OF THE INVENTION                      Matte paste for cationic paint system                              TECHNICAL FIELD OF THE INVENTION   The present invention relates to matte pastes for cationic paint systems.                              BACKGROUND OF THE INVENTION   Use synthetic porous silica to achieve a matte finish with paints, varnishes and lacquers. It is known. The use of silica in solution-based and water-based paints is particularly known. ing. The effect of silica on gloss reduction is due to the evaporation of solvents that occur during the drying of paints. This is usually accompanied by a decrease in coating volume.   Manufactures 100% solids coatings formulations that crosslink under UV light Wear. The coating contains oligomers, photoreactive initiators and various additives.   As the popularity of radiation-cured paints in various applications increases, gloss The ability to modulate and reduce the temperature is becoming more important. 100% solids UV In curable coatings, large amounts (up to 15% by weight) of porous silica or large Particle size silica is required to achieve a matte or semi-gloss finish. Because For example, does curing of UV-curable paints involve minimal shrinkage of the coating and no evaporation of solvent? It is. These practices rely on increasing the viscosity of the varnish when using high silica concentrations. Is limited or when a large amount of APS is used, Limited.   Uses three main types of photo-curable resins in UV-curable paint I) acrylated oligomers, ii) unsaturated Using ester and iii) alicyclic epoxide and bisphenol A epoxide obtain. Acrylated oligomers and unsaturated polyesters are Polymerizes and crosslinks when mixed with agents that produce free radicals when exposed to light . Alicyclic epoxides and bisphenol A epoxides can be used under ultraviolet light. Polymerized and crosslinked when mixed with a sulfonium salt which decomposes to form an acid catalyst to initiate the reaction Can bridge. The mechanism of this curing is “Cationic Curing” ) Is defined.   The gloss of paints containing acrylated oligomers and unsaturated polyesters is Successful reductions can be achieved using the above-described method.   In epoxy resin based coatings that cure according to a cationic mechanism Reduces the gloss of dry coatings even with silica of large particle size, even at very high concentrations. I will not reduce it. These paints have numerous applications due to their abrasion, hardness and heat resistance But not easily manufactured with matte or semi-gloss finish .   Therefore, there is a need for matting agent systems that can be used in cationically curable coating systems.   What has now been discovered is that, surprisingly, vinyl acetate is used with cycloaliphatic epoxy resins. Rare ethers (eg CHVE, DVE3) and acrylates (HDDA, TPGDA, DPGDA) Excipient The use of 10 to 40% by weight greatly enhances the action of the porous silica and has other desired effects. Cationic curing or hybrid curing (cationic / Can produce matte and semi-gloss paints based on free radical curing) .   Test method and definition   i Surface area with nitrogen-pore volume   Surface area with nitrogen is measured using ASAP2400 equipment supplied by Micromeritics, USA Using the multipoint method of Brunauer. Emmet. According to the standard nitrogen adsorption method of Teller (BET) Measurement. The sample is degassed under vacuum at 270 ° C. for at least 1 hour before measurement. Surface area is P / P₀ It is calculated from the capacity of the adsorbed nitrogen gas at 0.98. This device also Given the pore size distribution, the pore size (D_Ten) (10% of the pores are smaller than this pore size) ) Can be obtained. The pore size (D₅₀) And (D₉₀) (Pore 50% and 90% are below this pore size). Further given range Pore volume to pore size (cm^Three/ g) is also obtained from the desorption curve.   ii Weight average particle size   The weight average particle size was measured using a 100 mm path length lens. Measured using a Starsizer (Malvern Mastersizer). UK Worcestershire Manufactured by Malvern Instruments, Inc. Fraun using He / Ne leather The principle of Fraunhoffer diffraction is used. Put the sample in water for 7 minutes before measurement Disperse by sonication to form an aqueous suspension. Malvern Mastersizer The weight particle size distribution of Rica is measured. Weight average particle size (d₅₀), Decile (d_Ten) And 90 Quantile (d₉₀) Are easily obtained from the data generated by the device.   iii Matting efficiency   The following coating compositions were prepared by the following procedure to test the matting efficiency.   Composition:   UVR6110^*                          81.5-X%   Vinyl ether X   UVR6990^*                            3.0%   Fluorad FC340^♯          0.5%   Silica 15%   ^*  Obtained from Union Carbide   ^#  Obtained from 3M   Weigh the resin, diluent, additives and photoinitiator in a tan jar and mix (Coweles) 30 seconds at 500 rpm using a Heidolph stirrer with a head Stirred. Then silica was added and all components were stirred at 3000 rpm for 10 minutes. Profit Degas the applied paint system and then use a 25 micron K-bar applicator Spread over a black Leneta 7C card. 300W / inch fusion Use the Fusion H lamp to Cured at 3 m / min. Gloss at 60 ° is measured using a BYK multi-gloss meter And measured on the cured coating.   When X is 20%, the gloss of 60 ° measured in gloss unit is described as matte effect in the following description. Referenced as rate.                                Disclosure of the invention   A first object of the present invention is to provide a matting monomer and an amorphous silicone at a weight / weight ratio of 2 to 4: 1. Providing matte paste for use as matting agent in cationic paint system containing Rica To offer.   Amorphous silica used in the present invention is 1.0 to 2 as measured by nitrogen porosimetry. 2.0 ml / g, preferably at least 1.8 ml / g pore volume, 200-500 m^Two/ g surface area and Preferably have an average particle size of 4.0 to 12.0 microns as measured by Malvern. Good.   In another preferred embodiment of the present invention, the amorphous silica is silica coated with wax. The silica is 1.0-2.0 ml as measured by nitrogen porosimetry before coating. / g, preferably at least 1.8 ml / g pore volume, 200-500 m^Two/ g surface area and It has an average particle size of 4.0 to 12.0 microns as measured by Lubern. This concrete In the example, the wax coating preferably represents 6 to 15% by weight of the weight of the vermilion coated silica. New Wax should be microcrystalline wax (microwax) or polyethylene wax. It is also preferred that it is made of grease.   Matting monomers contain one or more functional groups Vinyl ether monomers and acrylates containing one or more functional groups It is also preferred that it is selected from the group consisting of monomers or mixtures thereof. Single for matting The monomer is triethylene glycol divinyl ether (DVE-3), 1,4-cyclohexa Dimethanol divinyl ether (CHVE), hexanediol divinyl ether, Ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, Hexanediol divinyl ether, tripropylene glycol triacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), 1,6-hexanedi All diacrylate (HDDA), trimethylpropane triacrylate (TMPTA), Ethoxylated trimethylpropane triacrylate (EO-TMPTA), propoxy Glycerol triacrylate (GPTA), triethylene glycol dia More preferably, it is selected from the group consisting of relates and mixtures thereof.   A second object of the present invention is to provide an epoxy resin of 40 to 80% by weight and a weight of 20 to 60% by weight. Providing a photocurable cationic coating system containing an amount of matte paste It is. Epoxy resin is alicyclic epoxy resin or bisphenol A epoxy resin Alternatively, it is preferably selected from the group consisting of these mixtures.   The third object of the present invention is to provide a gloss unit of 40 gloss units or less, preferably 30 gloss units or less. More preferably, an epoxy resin having a matting efficiency of 20 gloss units or less and a weight ratio of 40 to 80% by weight. Contains fat The present invention provides a photocurable and cationic coating system having the same. Epoxy resin is fat Cyclic epoxy resin or bisphenol A epoxy resin or a mixture thereof. It is preferable to be selected from the group consisting of                                Disclosure of the invention   The present invention is further described in the following examples.Example 1 (comparative example)   Used by continuous addition of various components or to add to the desired gloss paint Paint composition by forming a matte paste with the resulting silica and matting diluent Can manufacture things.   The control composition is as follows:   UVR6110^*           71.5% Alicyclic epoxy resin   Tone polyol^*                       10% polyol   UVR6990^*           3.0% cationic photopolymerization initiator   Fluorad FC430^#   0.5% flow additive   Silica 15%   ^*  Obtained from Union Carbide   ^#  Obtained from 3M   From this composition, a 25 micron film was coated on a Reneta 7C card with the silica of Table 1. Produced and cured at 3 m / min using one 300 W / inch Fusion H lamp And showed the glossiness.  ED30 (Syloid ED30 from WR Grace) and OK412 (Ace from Degassa) All silicas except Matt OK 412) are trade names of Gasil from Crossfield. It is a commercially available silica obtained.Example 2 (comparative example)   When compared to Example 1, another control coating composition without the tone polyol was used. Was.   UVR6110 86.5% Alicyclic epoxy resin   UVR6990 3.0% cationic photopolymerization initiator   Fluorad FC430 0.5% Flow additive   Silica 10%   Two silicas were tested and the gloss at 60 ° is as follows: Example 3 (the present invention)   Part X of CHVE or DVE was used in place of UVR6110 in the composition of Example 2. Occasionally, the gloss values in Table 2 were obtained for the following coating compositions.   UVR6110 81.5-X%   Vinyl ether X   UVR6990 3.0%   Fluorad FC430 0.5%   Silica 15% Example 4 (the present invention)   Similar results were obtained with another diluent, namely acrylate. This is Both a photoinitiator for on-curing and a photoinitiator for free radical curing This is the case for so-called “hybrid” paint compositions containing Have   UVR6110 86-X%   UVR6990 3.0%   Fluorad FC430 0.5%   Acrylic diluent X%   Irgacure 184^(a)          0.5%   Silica 10%   ^(a) Obtained from Ciba Geigy   In the composition, the acrylated diluents belong to the following group [1,6-hexanediol] Diacrylate (HDDA) and tripropylene glycol triacrylate (TPGDA) Irgacure 184 is a free radical photopolymerization initiator. set Table 3 shows the results obtained from the product 3.

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Claims (1)

A matting paste comprising a matting monomer and amorphous silica in a weight / weight ratio of 1.2 to 4: 1, and used as a matting agent in a cationic coating system. 2. Amorphous silica, 1.0～2.0Ml / g, preferably at least 1.8 ml / a g and a mean particle size of the surface area and 4.0 to 12.0 microns in pore volume and 200 to 500 m ² / g of, according to claim 1, wherein Matte paste. 3. Amorphous silica is silica coated with wax, the silica is pre-coated, as measured by nitrogen porosimetry 1.0~2.0ml / g, preferably a pore volume of at least 1.8m l / g, 200~500m ² A matte paste according to claim 1 having a surface area of / g and an average particle size of 4.0 to 12.0 microns as measured by Malvern. 4. 4. Matting paste according to claim 3, wherein the wax coating layer preferably represents 6 to 15% by weight of the uncoated silica. 5. The matting monomer is selected from the group consisting of a vinyl ether monomer containing one or more functional groups and an acrylate monomer containing one or more functional groups or a mixture thereof. 4. The matte paste according to range 2 or 3. 6. Matting monomers are triethylene glycol divinyl ether (DVE-3), 1,4-cyclohexane dimethanol divinyl ether (CHVE), hexanediol divinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, hexanediol divinyl ether, Tripropylene glycol triacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), 1,6-hexanediol diacrylate (HDDA), trimethylpropane triacrylate (TMP TA), ethoxylated trimethylpropane triacrylate (EO-TMPTA 6. The matte paste according to claim 5, which is selected from the group consisting of propoxylated glycerol triacrylate (GPTA), triethylene glycol diacrylate and mixtures thereof. 7. A photocurable cationic coating system containing 40-80% w / w epoxy resin and 20-60% w / w matting paste. 8. Light having a matting efficiency of 40 gloss units or less, preferably a matting efficiency of 30 gloss units or less, more preferably 20 gloss units and containing 40 to 80% w / w epoxy resin. Curable cationic paint system. 9. 9. The photocurable cationic coating system according to claim 7, wherein the epoxy resin is selected from the group consisting of an alicyclic epoxy resin, a bisphenol A epoxy resin, and a mixture thereof.