Classifications

• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols

Definitions

• the present invention relates to a method for continuously producing an emulsified water-based paint, and more particularly, to a carboxyl group-containing acrylic resin component, an epoxy resin component, and an epoxy resin.
• the present invention relates to a method for continuously producing an emulsified water-based paint containing a curing agent resin component for a resin.
• paints made of a combination of an epoxy resin and a curing agent resin, and vinyl paints The paint is excellent. These paints exhibit good performance when applied in the form of an organic solvent solution.However, during spray painting, the solvent evaporates into the working environment, resulting in air pollution and environmental health. Cause problems.
• the first type of such a water-based coating is to atomize the coating resin by some means, and to disperse the surfactant or water-soluble or hydrophilic resin in water as a dispersant. It is a dispersed one.
• the second type is to react a paint resin having a functional group, such as an epoxy resin, with a resin having a carboxyl group, such as an acrylic resin.
• the modified resin is self-emulsified in an aqueous medium by neutralizing the modified resin with ammonia or amines.
• Japanese Patent Application Laid-Open No. 59-213137.18 Japanese Patent Application Laid-Open No. 59-213137.18.
• the dispersed particle size of the paint resin is generally coarse or uneven, and the water-based paint is dispersed.
• the stability is poor, and the performance of the obtained coating film is inferior to that of the solvent type coating.
• the latter type of paint has great restrictions on the paint resin composition, even though it is superior in terms of dispersibility and the like to the former type of paint.
• the content of the resin curing agent it is difficult to make the content of the resin curing agent large enough, so that the coating film cannot be sufficiently cured. For this reason, there arises a problem that the hardness, the fineness of the coating film, and the nori- lation property with respect to corrosive components cannot be improved to a satisfactory level.
• the present inventors have previously described a carboxyl group-containing acrylic resin component, an epoxy resin component, and a curing agent resin for an epoxy resin.
• a solution of an organic solvent containing the components is prepared, and ammonia or amine is mixed with water in the solution, so that the carboxyl group in the acrylic resin is reduced to an ammonium salt.
• the resin component in the solution be converted into an amine salt and that the resin content in the solution be self-milked into an OZW emulsion.
• thermosetting resin containing an epoxy resin component and a curing agent resin component such as a resole type phenol resin, as an acrylic resin.
• a water-based paint is produced by phase-inversion emulsification utilizing the surface-active action, it has excellent curing performance, and has good adhesion to the paint film, hardness, denseness and corrosion components of the paint film. It has been found that a thermosetting paint having excellent barrier properties and the like can be obtained.
• the coatings formed using this paint may not always be able to achieve the smoothness and completeness of the coating at all times.
• the coating film formed by this paint has a tendency to form a block on its surface, As a result, the smoothness of the surface is reduced, and the degree of coating of the substrate is incomplete. This phenomenon was first discovered in the above-mentioned water-based paint containing the three components of the resin, but was completely recognized in conventional organic solvent-based paints. There was no problem.
• an object of the present invention is to provide a water-based paint in which the above-mentioned problems in the conventional water-based paint have been solved and a new method for producing the same.
• Another object of the present invention is to solve the above-mentioned drawbacks of the prior art and to use a relatively compact device to prepare a carboxyl group-containing acrylic resin component, an epoxy resin component and a curing agent therefor.
• An object of the present invention is to provide a method capable of continuously producing an emulsified paint from a resin component.
• Another object of the present invention is to provide a method capable of producing an emulsified water-based coating material having a high solid content and a small particle size with a relatively small amount of solvent and water, and a high efficiency. is there .
• an object of the present invention is to provide an emulsified aqueous solution containing a carboxyl-containing acrylic resin component, an epoxy resin component, and a resole-type phenol resin component as essential components.
• An object of the present invention is to prevent the occurrence of the above-mentioned bumps at the time of painting, and to improve the smoothness of the coating film and the completeness of the coating.
• the present invention in the form of an organic solvent solution containing a carboxyl group-containing acrylic resin component, an epoxy resin component and a curing agent resin component for an epoxy resin alone or in combination,
• the mixture is supplied to the first stage in-line mixer together with the aqueous solution of the monitor or amines, and mixed under pressure in the mixer to form a W-type emulsion.
• the WZO emulsion is supplied to the second stage in-line mixer together with the water, mixed in the mixer and phase-converted into an OZW emulsion to produce.
• the present invention provides a continuous production method of an emulsion type water-based paint characterized by quantitatively extracting a W-type emulsion.
• a carboxyl group-containing acryl resin component, an epoxy resin component and a resole type phenol resin component as film-forming components
• the carboxyl group of the acrylic resin component is present in the form of an ammonium salt or an amine salt
• the film-forming component is formed of ozw-type emulsion ion particles.
• An emulsified water-based paint that exists in the form of an alkylate resin in which at least 30 mol% of all methylol groups in the resin-type phenolic resin component are alkylated.
• the present invention provides an emulsified water-based paint characterized in that:
• the etherified compound of the resole-type phenol resin component is a petroleum compound.
• the resole-type phenol resin component is a dinuclear resin. It is particularly useful when the composition contains a low-molecular-weight substance consisting of an isomer and a mononuclear body in an amount of 10 to 98% by weight, particularly 20 to 95% by weight.
• FIG. 1 is a schematic layout view of an apparatus used in the continuous production method of the present invention.
• an organic solvent solution containing a carboxyl group-containing acrylic resin component, an epoxy resin component, and a curing agent resin component for an epoxy resin alone or in combination (hereinafter simply referred to as a resin solution)
• the resin solution is supplied to the first stage in-line mixer together with the ammonia or the aqueous solution of the amine and mixed under pressure to temporarily
• a WZO-type (water-in-oil) emulsion This WZO-type emulsion is supplied together with water to a second-stage in-line mixer and mixed. Reversible to OZW type (oil-in-water) emulsification; and quantitative extraction of ozw type emulsion generated by phase inversion is remarkable. It is a feature.
• the present invention provides a wzo-type emulsion in which a resin solution is mixed with an aqueous solution of ammonia or amine before water inversion, and water is dispersed in the resin solution in a fine particle size.
• emulsion from resin solutions is based on acrylic resin.
• Exists in a state compatible with other paint resins and in a state of being copolymerized with a blend or an epoxy resin-forming component, but the carboxyl group in the acrylic resin component is It is carried out by being neutralized with added ammonia or ammonia and directing it in the form of salt to the interface with water.
• ammonia or amine necessary for the neutralization is added in the first step of producing the WZO-type emulsion.
• the phase transition from the WZO type to the OZW type is performed with a simpler mechanism.
• the mixing of the resin solution with ammonia water or ammonia water and the mixing of the water type 0 emulsion with water are carried out intimately.
• the mixing of the resin solution with ammonia water or ammonia water is carried out under extremely high viscosity conditions, thus preventing cavitation. To do this, use force ⁇ .
• By forming the emulsion it is possible to convert the phase into a uniform and fine 0W-type emulsion.
• FIG. 1 is a schematic layout of an apparatus used in the continuous production method of the present invention.
• this apparatus is composed of a first processing tank 1 and a second processing tank 2.
• the first treatment tank 1 is for forming a W-type 0 emulsion, and has an in-line mixer 3 therein.
• the second treatment tank 2 has no W type It is for forming an emulsion and has an in-line mixer 4 inside.
• the first treatment tank 1 is provided with a resin solution supply line 5, an ammonia water or ammonia water supply line 6, and a pressure line 7 in the tank.
• the first processing tank 1 and the second processing tank '2 communicate with each other via a communication pipe 8.
• the second treatment tank 2 is further provided with a water supply line 9 and a product withdrawal line 10, and the product withdrawal line 10 has a fixed amount.
• Discharge valve 11 is provided.
• the resin solution is supplied to the first treatment tank 1 through the supply line 5 and the ammonia water or the amine water is supplied to the first treatment tank 1 through the supply line 6, respectively.
• a pressurized fluid such as nitrogen, air, water vapor or the like is supplied to the tank 1 from the pressurized line 7 and pressurized to a predetermined pressure.
• the in-line mixer 3 is driven, and the two are mixed under pressure to produce a W0-type emulsion 12.
• the formed WZO emulsion 12 is sent to the second treatment tank 2 through the communication pipe 8. Water is supplied to the second treatment tank 2 via the water supply line 9, and the WZO type emulsion and water are mixed by the inline mixer 4, and the OZW type emulsion is mixed.
• Phase 13 is generated by phase inversion.
• the generated 0 / W-type emulsion 13 is quantitatively taken out of the apparatus as a product via the extraction line 10 and the quantitative discharge valve 11.
• the first treatment tank 1 is pressurized, and the first treatment tank 1 and the second treatment tank 2 are connected via the communication pipe 8.
• the WZO-type emulsion corresponding to the 0 / W-type emulsion discharged from the second treatment tank 2 Is sent from the first processing tank 1 to the second processing tank 2, so that the two-stage processing is performed smoothly or continuously.
• the coating solution used in the present invention contains three components, an acrylic resin component, an epoxy resin component, and a curing agent resin component for an epoxy resin.
• the acrylic resin component containing the carboxyl group and the epoxy resin component may be contained in the solution in the form of a copolymer, or the carboxyl group may be used.
• a silyl-containing acrylic resin component and an epoxy resin component may be contained in the solution in the form of a blend.
• the acid value of the acrylic resin should be in the range of 35 to 350, especially 70 to 330, and this acrylic resin should be used as the coating resin. It is generally preferred to use it in an amount of up to 30% by weight, in particular 5 to 25% by weight.
• the neutralization step and the subsequent phase change emulsification step described below reduce the paint resin to a fine particle size.
• the acid value of the acrylic resin is higher than the above range, the acrylic resin tends to separate from the paint resin in a later step and move to the aqueous phase. This makes it difficult to emulsify the particles to a fine and uniform particle size, and also decreases the stability of the dispersion.
• the resulting coatings have the disadvantage of being more sensitive to humidity.
• the present invention by selecting the acid value of the acrylic resin within the above range, the emulsification of the paint resin into a uniform and fine particle size and the improvement of the dispersion stability of the emulsified resin are achieved. This makes it possible to obtain a coating film having excellent moisture resistance, water resistance and the like.
• the amount of the acrylic resin is less than the above range, the interface between the water phase and the oil phase (resin phase) is carried out in the neutralization step and the subsequent phase change step. Insufficient carboxylate groups can be formed, making it difficult to emulsify the paint resin to a uniform and fine particle size, and to stabilize the dispersion of the aqueous dispersion. Will also decrease.
• increasing the amount of the acrylic resin to be mixed beyond the above range means that a large amount of the acrylic resin is mixed into the coating resin, and thus the coating properties are increased. Therefore, it is recommended that the amount be within the above range.
• the acrylic resin includes an ethylenically unsaturated carboxylic acid or an anhydride thereof, which gives the above-mentioned carboxylic acid group having a carboxyl group in the resin, and an acrylate ester or an acrylate ester. It comprises a copolymer of a methacrylate and, if desired, another ethylenically unsaturated monomer copolymerizable therewith.
• the ethylenically unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, crotonic acid, maleic acid, and fumaric acid. Acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride and the like.
• esters of acrylic acid / methacrylic acid include (meth) acrylic acid methyl ester and (meth) acrylic acid ethyl phenol. , (Meta) acrylic acid acrylate mouth pill, (meta) acrylic acid n-butyl, (meta) isobutyl acrylate, (meta) Acrylic acid n-amyl, (meta) isoamyl acrylate, (meta) acrylic acid n-hexyl, (meta) acrylic acid Acid 2—ethyl hexyl, (meth) acrylic acid n—year-old octyl, etc.
• the above-mentioned (meth) acrylic acid means acrylic acid or methacrylic acid.
• comonomers that are copolymerized with these monomers include styrene, vinyl toluene, acrylonitrile, Relonitrile and the like can be mentioned.
• the acrylic resin used should have a molecular weight sufficient to form a film, and is generally between 10,000 and 200,000, especially between 20,000 and 150, Desirably, it has a molecular weight in the range of 000.
• Suitable combinations of acryl copolymers include (1) methyl methacrylic acid 2-acrylic acid 2-ethylhexyl acrylic acid, (2) Methyl styrene methacrylate, (3) Ethyl methyl acrylate, (3) Methyl styrene acrylate Tacrylic acid, (4) methylacrylic acid methylnoacrylic acid ethylnoacrylic acid, etc.
• acrylic resins convert these monomers into organic solvents.
• azobisisobutyronitrile is easily obtained by polymerizing in the presence of a peroxide.
• Epoxy resins include bisphenols obtained by the polycondensation of bisphenols such as bisphenol A with pinodurohydrin.
• the epoxy equivalent is generally in the range of from 400 to 20,000, especially from 1,000 to 5,000, and the number average molecular weight is from 1 to 5,000. It is preferably in the range from 2,000 to 20,000, especially from 2,000 to 13,000.
• the resin curing agent that is reactive with the epoxy resin examples include a functional group having a reactivity with a hydroxyl group or an oxylan ring of the epoxy resin, such as a hydroxyl group.
• Resin having amino group, carboxyl group, etc . For example, resole type and phenolic or phenolic phenol resin, urea resin Lum aldehyde resin, melamine / holm aldehyde resin, alkyd resin, polyester resin, acryl resin, polyurethane resin, key One or a combination of two or more of styrene resin, epoxy resin, and petit resin are used.
• a methylol group-containing thermosetting resin described later, particularly a resole type phenol resin is preferable.
• the coating resin is finely divided. It can be emulsified and dispersed to a dispersed particle size.
• the ratio of the epoxy resin to the curing agent resin is in the range of 95: 5 to 40:60 by weight, especially in the range of 90:10 to 50:50 by weight. Is common.
• each resin component may be present as a simple mixture, or may be present as a precondensate or a copolymer.
• the epoxy resin component and the acrylic resin component may be a blend or may be present in the form of a copolymer.
• the copolymer should have a free carboxyl group.
• the acid number per resin as a whole should generally be in the range from 2 to 30, in particular from 5 to 20. Suitable examples of the epoxy-acrylic copolymer are described in JP-B-59-37026.
• an acrylic resin component ii) an epoxy resin component, and iii) a curing agent resin are used.
• the curing agent resin is a resole-type phenolic resin, and the resole-type phenolic resin component is at least 30 mol% of all the methylol groups, especially 4%.
• the use of a resin-type phenolic resin component in which 5 to 90 mol% is alkylated eliminates the occurrence of the above-mentioned bubbling on the coating film surface. However, the smoothness of the formed coating film and the completeness of the coating are remarkably improved.
• These low molecular weight components such as mononuclear and dinuclear have a high curing rate with respect to the epoxy resin component, and are also involved in improving the adhesion of the substrate. It is an indispensable component for water resin. These low molecular weight components are soluble in the ammonia or the water containing the amine added during emulsification and, therefore, in the form of a solution in aqueous paints. It is believed to exist. When this water-based paint is applied to a substrate to form a wet coating film, water evaporates on the surface immediately after the formation of the coating film. It is considered that the molecular weight component causes the coating film forming resin to salt, and this is the cause of the occurrence of a bump on the coating film surface.
• the above-mentioned mononuclear or dinuclear isomers are obtained.
• the solubility of the low molecular weight component in water or the amount of water soluble in water is suppressed, and the salting out of the film-forming resin component is prevented, and as a result, It is believed that the occurrence of fuzz is suppressed.
• Resin-type phenolic resins include phenolic carbonate, p-cresol, m-cresol, o-cresol, and p-tert-butylphenol.
• An initial condensate obtained by condensing aluminum aldehyde with an aluminum catalyst in the presence of an Alkali catalyst is used.
• an initial condensate having a number average molecular weight of 150 to 100000 is used.
• R is an alkyl group
• a methylol group in the resin is converted into a null catalyst by an etherification catalyst, especially an acid. It is performed by reacting in the presence of a catalyst.
• alcohols examples include methanol, ethanol, and n. Or iso-bromo-nor, n-, iso-, tert-butanol, etc., but alcohols with 3 to 6 carbon atoms can be used. Butanol, especially butanol, is preferred.
• the etherification catalyst use is made of phosphoric acid, sulfuric acid, hydrochloric acid, aromatic sulfonic acid (for example, P-toluenesulfonate), oxalic acid, acetic acid, etc. You can do it.
• the dissolved thermosetting resin having a methylol group and alcohol are reacted in a suitable solvent in the presence of the catalyst.
• the amount of the catalyst used is such that the pH of the reaction system is 4 to 6, and the reaction temperature is preferably in the range of 70 to 90 ° C.
• the solvent an excess of alcohol, toluene, xylene or the like is used alone or in combination.
• the water in the reaction system is azeotropically distilled with a solvent. It is desirable to carry out the reaction while taking it out of the system in the form of. Of course, when the amount of alcohol in the system is insufficient, it may be added to the reaction system.
• the production of the phenolic resin and the alkyl ether can be carried out in the same step or in separate steps.
• the reaction between phenols and formaldehyde is carried out in a medium containing alcohol in the presence of an aluminum catalyst to form a desired methylol.
• an acid catalyst can be added to the system to carry out an alkyl etherification reaction while maintaining the pH.
• the methylated resin to be formed is separated by a method known per se, and this is separated in another system into an alkyl ether. You can do Luihi.
• the obtained alkyl etherified resin may be neutralized, washed with water, and dried to be used as a film-forming resin component, or may be formed by some means such as a salt generated by the neutralization. It may be removed and used as it is in the form of a resin solution.
• the present invention is capable of emulsifying and dispersing this coating resin to a fine dispersed particle size even when the composition ratio of the epoxy resin and the phenol resin is within an arbitrary range.
• the ratio of the epoxy resin to the phenol resin is within a weight ratio of 95: 5 to 40:60, particularly a weight ratio of 90:10 to 50:50. Generally, there is.
• the acrylic resin as a polymer dispersant has an acid value of 2 to 30, especially 5 to 20 on the basis of the coating resin component, and 3 to 3 of the total coating component. It is important that it be present in an amount of 0% by weight, in particular 5 to 25% by weight. If the acid value is below the above range, it becomes difficult to disperse the resin component in the form of a 0 ZW emulsion, and even if it is strongly dispersed, Poor dispersion stability. When the acid value exceeds the above range, the hot water resistance of the coating film as a paint for cans decreases, and the corrosion resistance and the like after retort sterilization decrease.
• Resin component and Precondensation may be carried out with the phenolic resin component, or the acryl resin component and the epoxy resin component may be cooked to form a carboxylate. It can also be used as an excess of an acrylic resin-epoxy resin copolymer.
• the above-mentioned three components are used as a high-viscosity resin solution, continuous production of the emulsified water-based paint is possible, and the method for producing an emulsified water-based paint according to the present invention is described above. It is preferable to use them for the three components.
• the use of an alkyl etherified resin as the above-mentioned resin-type phenolic resin allows the resin-coated phenolic resin to be applied to the surface of the coating film. The occurrence of bubbling is eliminated, and the degree of smoothness of the coating film and the degree of completeness of the coating can be significantly improved.
• organic solvent for the resin solution examples include aromatic hydrocarbon solvents such as toluene and xylene: acetate, methylethylketone, methylisobutylketone, and the like.
• Ketonic solvents such as cyclohexanone: alcohol solvents such as ethanol, pronoanol, and butanol: ethyl solvents, butyr
• cellulosic solvents such as lucose mouth solvent
• ester solvents such as ethyl acetate and butylacetate
• the resin concentration in the raw material solution is generally in the range of 5 to 80% by weight, particularly preferably in the range of 20 to 70% by weight.
• This raw material solution may be blended with a known paint compounding agent, for example, a plasticizer, a lubricant, a pigment, a filler, a stabilizer, and the like, as desired.
• the amines used for neutralization include alkylamines such as trimethylamine, triethylamine, n-butylamine, and '2-dimene. Chill Amino Ethanol, Dietanol Amin, Trie Alumina Amin, Amino Methyl Chloropanol, Dimethyl Amino Methyl Methyl Brono Alcohol amines such as knoll are used. Also, polyvalent amines such as ethylamine and methylentriamine can be used. Further, an amine / complex amide having a branched alkyl group is also preferably used.
• Examples of the amine having a branched-chain alkyl group include isopropylamine, sec-bunalamine, tert-butylamine, and isoamine.
• As the complex amide a saturated heterocyclic amide containing one nitrogen atom such as pyrrolidine, piperidine, and morpholine is used.
• Ammonia and amines should be used in an amount of at least 0.3 chemical equivalent, especially 0.7 to 1.3 chemical equivalent, based on the carboxyl group of the acrylic resin.
• A: B 10: 10 to 10: 1
• the wzo-type emulsion is not generated stably without the ozw-type. Since the phase is changed to emamulsion, the particle size of the disperse phase of the ozw-type emamulsion to be formed tends to be coarse, and the liquid volume is in the above range. If the amount is less, it is necessary to add a relatively large amount of water when converting the generated w-type 0 emulsion to the ozw-type emulsion. First, the phase inversion tends to be unstable, and the particle size of the dispersed phase tends to be uneven.
• the degree of pressurization was generally between 0,2 and 10 Kg. / cm 2 (gauge), especially 0.5 to 7 Kg / cm 2 (gauge).
• the temperature at the time of mixing is generally in the range of 10 to 90 ° C, particularly preferably in the range of 15 to 70 ° C.
• the mixing in the first stage does not involve a neutralization reaction, and the force is vigorous stirring, and the temperature may rise to 100 ° C or more due to heat generation. This should be understood. Of course, it is possible to heat from the outside when high temperature is desired, or to cool from external force when temperature rise is not desired. Wear .
• the degree of mixing by the first stage in-line mixer is determined by the formula
• V represents the supply amount Z min) to the in-line mixer
• V 2 represents the in-line mixer Indicates the discharge rate (min) measured using the water of the stirrer.
• the stirring efficiency (K) defined by the formula (5) should be 5 to 50, especially 7 to 35. If the K value is smaller than the above range, there may be cases where a uniform and fine W0-type emulsion cannot be formed, while the K value may be smaller than the above range. If it is larger than the range, the production rate of the water-based paint tends to be low, and it tends to be less industrial.
• the W / No. 0 emulsion produced in the first step is supplied to a second-stage in-line mixer together with water to form a 0 / W type emulsion.
• the phase is changed to.
• the amount of water used in the second step depends on the amount of water in the WZO-type emulsion from the first step.
• the amount is such that the phase conversion into the solvent is sufficiently carried out, and is generally in the range of 100 to 100 parts by weight of WZ0 emulsion, 30 to 100 parts by weight of water, particularly 35 to 8 °. It is the weight part.
• This phase inversion process is easier to perform than the WZO-type emulsion generation process of the first process, and there are no particular restrictions on temperature and time, but the W-type 0 emulsion process of the first process. Since the OZW-type emulsion is communicated with the second-stage OZW-type emulsion, it is performed under almost the same temperature and pressure conditions.
• the generated 0 W emulsion is quantitatively discharged to the outside through a quantitative discharge valve.
• This quantitative emission May be carried out continuously at a constant flow rate or intermittently at certain times.
• the aqueous dispersion contains both water and an organic solvent.
• the organic solvent can be removed by azeotropic distillation with water, and the aqueous dispersion can be concentrated.
• the azeotropic distillation of the organic solvent can be carried out with external water supply.
• the concentration of the paint resin solids in the final water-based paint should be in the range of 10 to 70% by weight, especially in the range of 20 to 60% by weight, and in the water-based paint.
• the content of the organic solvent is preferably 15% by weight or less, particularly preferably 5% by weight or less. Further, for the purpose of improving the dispersion stability of the resin component in the paint, it is permissible to add a small amount of a surfactant or a polymer dispersant to the system at an arbitrary stage.
• the water-based paint according to the present invention has a viscosity suitable for coating, and can be used for applying various metal materials, can bodies, can lids or other members.
• This water-based paint is not used for ordinary spray coating and electrostatic coating, but is used for roller coating, brush coating, and doctor coating. First, it can be used for dispensing work with various coaters such as air life coat and reverse coater.
• a coating solution containing an acrylic resin component having a carboxyl group is mixed with ammonia water or amine water.
• Aqueous emulsified paint with a very fine and even particle size from a remarkably high-viscosity resin solution by linking with the process of phase inversion into a mold emulsion. Can be manufactured continuously. For this reason, according to the present invention, it has become possible to produce an aqueous emulsified coating material having a high solid content with a high efficiency with a relatively small amount of solvent and water.
• the emulsified water-based paint to be tested was placed in a 100 m £ glass wide-mouthed bottle with a capacity of 100 m £, sealed, and stored in a thermostat at 50 ° C for one month. After opening the container, it was inspected, and the presence or absence of skinning on the liquid surface, the viscosity of the emulsified water-based paint, and the average particle size of the resin particles were examined and compared with those before storage.
• the emulsified water-based paint to be tested is applied to an electrolytic chromic acid-treated steel sheet (hereinafter referred to as TFS) using a roll coater, baked at 210 ° C for 10 minutes, and cured.
• TFS electrolytic chromic acid-treated steel sheet
• the coating thickness was about 5 m. Visual inspection of unevenness on the painted surface of this painted plate It was evaluated more.
• the above coated plate was cut into 5 m m width, in the this that push push 2 minutes Na A B emission system E Tsu Bok blanking Les scan which have use an adhesive which is heated in 2 0 0 ° C of Glued.
• the peel strength was measured using a T-peel, and the initial peel strength immediately after bonding and the peel strength with time after immersion in warm water at 90 ° C for one week were determined.
• a part of the coated plate was subjected to a rettling treatment at 125 ° C. for 30 minutes, and the presence or absence of whitening of the coating film by the retret treatment was examined.
• test water-based paints For some emulsified water-based paints, apply the test water-based paint to one side of the TFS with a mouthcoater, bake and dry at 210 ° C for 10 minutes, and then dry. One side was similarly painted and baked to prepare a double-sided painted plate. The thickness of each coating film was about 4 m.
• a 202 diamond glue can both ends are neck-in processed to form a 200 diamond) ) was prepared, the canopy was double-sealed, the contents were filled, the bottom lid was double-sealed, and the can was packed in a can.
• the cans were subjected to retort sterilization at 120 ° C for 90 minutes, cooled, air-dried, and stored in a warehouse. After storage for 6 months, they were opened and inspected for abnormalities such as whitening of the coating and internal corrosion. In addition, some of the coated plates were formed into can lids and used for evaluation.
• the discharge amount of the stirrer in the in-line mixer is as follows. It was measured in the manner described above.
• the first treatment tank 1 is fixed independently, the resin solution supply line 5 is closed, and the ammonia water or amine water supply line 6 is fixed in the water tank. Tube 8 must be open.
• the stirrer pumps up the water in the water tank and discharges the water drawn from the communication pipe 8. After the operation has reached a steady state, the water discharged through the communication pipe 8 during a certain period of time is collected, and its volume is measured. The discharge rate was determined.
• 200 parts were mixed solvent of xylene, methylisobutylketon, and cyclohexanone (xylene / methylisobutylbutylketone Z cyclohexane).
• Non 1/1/1
• a solution dissolved in 400 parts was prepared and mixed with the above epoxy resin solution.
• the mixture was added dropwise, copolymerized, and further stirred with the addition of 1 part of tert-butyl hydroperoxide at the same temperature for 3 hours.
• the reaction was completed by adding 500 parts of a solvent and cooling.
• the weight average molecular weight of the obtained acrylic resin was about 120,000, the acid value was 124, and the solid content of the resin solution was 50%.
• the above-mentioned acrylic resin solution was added at a ratio of 20 parts to 160 parts of the mixed solution of the epoxy resin and the phenol resin, followed by stirring.
• the mixture was uniformly mixed to obtain a coating resin solution in an organic solvent.
• an amine water was prepared by dissolving 90 parts of deionized water and 4 parts of dimethyl ether aminoethanol as a medium chemical. . Further, deionized water to be supplied to the second stage treatment tank was prepared.
• the discharge rate measured using water from the stirrer in the first-line inline mixer was set at 25 £ min, and the organic solvent solution of the coating resin was reduced to 1 using a metering pump. .8 l / min and ammonia water were supplied to the first-stage treatment tank at a rate of 0.95 lb / min, and the stirrer was driven. The pressurized line in the tank was closed.
• the discharge amount of the stirrer in the second-stage processing tank was set to 20 pounds per minute, and deionized water was introduced into this tank at 1.45 pounds per minute.
• the stirrer was operated while supplying with.
• the discharge rate from the second treatment tank was adjusted to about 4.2 & / rain by adjusting the constant discharge valve. As a result, the internal pressure of the treatment tank became about 1.2 Kg / cm 2 in gauge.
• the stirring efficiency of the first-stage in-line mixer was about 9.1, and the stirring efficiency of the second-stage in-line mixer was about 4.8.
• Table 1 shows 10 kinds of amines shown in Table 1 as neutralizing agents, and 10 kinds of emulsified water-based paints (according to the production method of paint 1) are used except for each of the 10 kinds of amines. Paints 2 to 11) were prepared. Table 1 also shows the average particle size of the resin particles of the obtained emulsion type water-based paint.
• An organic solvent solution of the coating resin used in Example 1, amide water, and deionized water were prepared. These were supplied to the first and second treatment tanks at the ratios shown in Table 2, respectively, in the same manner as in Example 1 except that seven types of emulsified water-based paints (Paint 1) were used. 2 to 18) were prepared. At this time, the stirring efficiency in the first-stage in-line mixer and the internal pressure of the treatment tank were determined by comparing the average particle size of the dispersed phase in the obtained 0-W type emulsion. Both are also listed in Table 2.
• An organic solvent solution of the coating resin used in Example 1, amine water, and deionized water were prepared. These are supplied to the first-stage and second-stage treatment tanks, respectively, and the rotation speed of the first-stage stirrer is adjusted to discharge the stirrer in the in-line mixer. Except for adjusting the output, six types of emulsified water-based paints (paints 19 to 24) were prepared in the same manner as in Example 1. At this time, the stirring efficiency in the first-line in-line mixer, the internal pressure of the processing tank, and the temperature of the liquid in the processing tank were determined based on the obtained OZW type emulsion fraction. The average particle size of the dispersed phase is shown in Table 3.
• Example 1 160 parts of the epoxy resin solution prepared in Example 1 and 40 parts of the acrylic resin solution were mixed, and further 5 parts of morpholine was added. The epoxy resin and the acrylic resin were reacted with each other by stirring for 90 minutes in the, to obtain a copolymer.
• amiin water and deionized water were prepared.
• Example 5 Using these, a 0 W type emulsion was prepared according to the method described in Example 1, and further concentrated and desolvated to obtain an emulsified water-based paint (paint 25). The average particle size of the dispersed phase of this emulsified water-based paint was 0.52 m. When its stability over time was examined, no skininess was found on the liquid surface. Neither the viscosity nor the average particle size of the resin particles had changed compared to before storage. Further, the paintability when coated with a roll coater was evaluated. As a result, the paintability was good, and the unevenness of the painted surface was at a level that did not hinder practical use.
• Example 5 Example 5
• Example 4 Using the organic solvent solution of the coating resin used in Example 4, the amide water, and the deionized water, supply the deionized water to the second-stage in-line mixer.
• Six types of 0 W type emulsions were produced in accordance with Example 1 except that the amount of water was adjusted.
• Deionized water supplied to the second stage in-line mixer per 100 parts of the W / 0 type emulsion supplied to the second stage in-line mixer The amounts are shown in Table 4. Further, Table 4 also shows the average particle size of the dispersed phase of the obtained 0 / W type emulsion.
• the organic solvent solution of the coating resin of Example 1 was concentrated at 80 ° C. using a rotary vaporizer to obtain a solution having a solid content of 60%, 70%, and 80%. It was prepared. Further, butyl acetate was added to the organic solvent solution of the coating resin of Example 1. By further diluting, solutions having solid contents of 10%, 20% and 30% were prepared. These solutions were converted into OZW-type emulsions using morpholine as a neutralizing agent according to the method shown in Example 1. At this time, the organic solvent solution of the coating resin was heated or cooled and supplied. In addition, the inside of the treatment tank was pressurized in order to perform stirring and mixing efficiently.
• Table 5 shows the temperature of the organic solvent solution of the coating resin and the internal pressure of the treatment tank supplied to the in-line mixer. Further, these OZW-type emulsions were concentrated and desolvated to obtain emulsified water-based paints (Paints 32 to 37).
• Table 5 also shows the results of evaluating the average particle size and the temporal stability of the resin particles of these emulsified water-based paints.
• the four types of curing agent resins shown in Table 7 were dissolved in the same manner as in Example 1, and an organic solvent solution of a coating resin was prepared using the epoxy resin solution and the acrylic resin of Example ⁇ . . Except for using sec-butylamine as an organic solvent solution of these coating resins and a neutralizing agent, four emulsifying water-based coatings (according to the method described in Example 1) were used. Paints 44 to 47) were prepared.
• a resin solution was prepared by mixing the epoxy resin of Example 1 and the phenolic resin in the ratios shown in Table 8, and the resin solution of Example 1 was prepared.
• the acrylic resin solution was added to obtain an organic solvent solution of a coating resin.
• the dissolution of the epoxy resin and the phenol resin was the same as in Example 1, and the amount of the acrylic resin solution added was the same as in Example 1 in terms of resin solids.
• six types of emulsified water-based paints (paints 48 to 53) were prepared according to the method described in Example 1 except that morpholine was used as a neutralizing agent. .
• Example 220 parts of a mixed solution of the epoxy resin solution and the phenol resin solution of Example 1, 10 parts of the acryl-based resin solution of Example 1, and 5 oleic acid The parts were uniformly stirred and mixed to obtain a coating resin solution in an organic solvent.
• a non-W-type emulsion emulsion was obtained by using poramine, which is an isocyanate mouth, as a neutralizing agent, and further concentrated and desolvated to obtain an emulsified aqueous paint. (Paint 62).
• This emulsified water-based paint has an average resin particle size of about 0.56 wm, does not settle even after being stored at 50 ° C for one month, and has a remarkably thick skin. No change has occurred.
• this phenolic resin has one or two benzene rings. Check that the ingredients are contained at 26%. confirmed. This phenol resin solution was stirred under reflux at 115 ° C for 2 hours to convert some of the methylol groups in the phenol resin into butyl ether. Let me know. Analysis by nuclear magnetic resonance (hereinafter abbreviated as NMR) showed that 68% 'of all methylol groups had been butyl etherified.
• NMR nuclear magnetic resonance
• the remaining amount of the above-mentioned monomer mixture was dropped into the mixture over 3 hours to copolymerize, and 0.1 part by weight of tert-butyl hydroperoxide was further added. Then, stirring was continued at the same temperature for 3 hours, and then 50 parts by weight of ethyl alcohol was added and cooled to complete the reaction. It was.
• the weight average molecular weight of the obtained acrylic resin was about 120,000, the acid value was 124, and the solid content of the resin solution was 50%.
• ammonia water was prepared by dissolving 6 parts by weight of ammonia water having a concentration of 28% in 450 parts by weight of deionized water, and the above epoxy resin and the epoxy resin were prepared. The whole amount of the mixed solution of the phenolic resin and the acrylic resin was gradually dropped into the vigorously stirred solution.
• the viscosity of the system increases to form a white cream, but as the addition of ammonia water progresses, the viscosity of the system gradually decreases. Begins to decline.
• the addition of the ammonia water was interrupted, and the stirring was continued.After the whole was dispersed uniformly, the addition of the ammonia water was restarted. The viscosity of the system dropped sharply.
• a stable 0 / W type emulsion was formed after the dropping of the entire amount was completed.
• This emulsion is concentrated at the mouth of a tally enopole, and about 300 parts by weight of water and about 200 parts by weight of an organic solvent are collected to obtain a solid content. 40%, and then filtered through a # 1 glass filter to obtain an emulsified water-based paint (water-based paint 101).
• This emulsified water-based paint has an average particle size of resin particles of 0.61 Aim, and contains 3.6% of an organic solvent per paint.
• the emulsified water-based paint was experimentally performed in the notch form as described above, but a similar emulsified water-based paint was obtained even when the continuous paint manufacturing apparatus of Example 1 was used. .
• the emulsified water-based paint was applied to electrolytic chromic acid-treated steel sheet (hereinafter referred to as TFS) using a roll coater and baked at 210 ° C for 10 minutes to cure. . Upon visual inspection of the painted surface, no buds were found.
• TFS electrolytic chromic acid-treated steel sheet
• the coated plate was adhered by pressing the hot plate heated to 200 mm with a nylon adhesive for 2 minutes.
• the peel strength was measured by T-peel, the initial peel strength immediately after bonding was approximately 7.1 kg / 5 min.width, and peeled over time after immersion in warm water at 90 for 1 week. The strength maintained a value of 4.5 Kg / 5 mra width or more.
• this adhesive test piece was subjected to a liter treatment at 125 ° C. for 30 minutes and evaluated, no whitening of the coating film was observed, and the width was 4-5 kg / 5 mm width. The above bonding strength was maintained.
• An emulsified water-based paint (comparative paint 20) was used in the same manner as in Examples 1 and 2, except that the resole-type phenolic resin used in Example 12 was used without being subjected to butyl etherification. 1) was made.
• This water-based paint was applied to TFS using a mouth coater, and visually observed after baking. As a result, the surface of the coating film was found to have noticeable bumpy irregularities. The painted appearance was inferior to that of the painted plate prepared in the above.
• Bisphenol A type epoxy resin with a number average molecular weight of about 3400 and an epoxy equivalent of about 110 A part of the solution was prepared and mixed with 80 parts by weight of the acrylic resin solution of Example 12. This mixed solution is charged into a four-neck flask, and while stirring, 16 parts by weight of acetylaminoethanol is added to the mixture to form a carboxyl group in the acrylic resin. Was neutralized, and the liquid temperature was raised to 80 ° C. After stirring was continued at the same temperature for 30 minutes, the mixture was cooled to room temperature. GPC measurement confirmed that the epoxy resin and the acrylic resin were copolymerized and the molecular weight was increased.
• an infrared spectrophotometer confirmed the presence of an amine salt of an epoxy group and a carboxyl group.
• 240 parts by weight of the above copolymer resin solution and 60 parts by weight of a solution of the butanol etherified resin phenolic resin of Example 12 were mixed, and An emulsified water-based paint (water-based paint 102) was produced according to Example 1 and Example 12.
• the average particle size of the resin particles in this emulsified water-based paint was 0.58 m, the solid content was about 49%, and the organic solvent content was 4.6% per paint.
• This emulsified water-based paint was applied to TFS using a roll coater and baked at 210 ° C. for 10 minutes to be cured. Visual inspection of the painted surface did not reveal the presence of a bud.
• the emulsified water-based paint (comparative paint 20) was prepared in the same manner as in Example 13 except that the resin phenolic resin used in Example 12 was used without being subjected to butyl etherification. 2) was fabricated. This water-based paint was applied to TFS using a roll coater and visually inspected after baking. When the coating was observed, block-like irregularities were noticeable on the surface of the coating film, and the film was prepared in Example 13. The painted appearance was inferior to that of the painted plate.
• Resole-type phenolic resin was synthesized using P-cresol and formaldehyde as raw materials and using a catalyst of hydroxymagnesium.
• the number average molecular weight of the obtained phenol resin was 350, and it was confirmed that 56% of a component having 1 to 2 benzene rings was contained.
• This phenol resin solution was dissolved in the same solvent as in Example 12, and the mixture was stirred under reflux at 115 C for a predetermined time, whereby a part of the methylol groups in the phenol resin was obtained.
• Example 12 Using the solution of the alkyl ether phenolic resin and the solution of the epoxy resin and the acrylic resin of Example 12, the method shown in Example 12 was used. Five types of emulsified water-based paints (water-based paints 109 to 113) were prepared in the same manner.
• Table 12 shows the number average molecular weight of these phenolic resins and the content of the components having one or two benzene rings (the content of low molecular weight components). 50 parts by weight of these were mixed with xylene and methylisobutylketone, cyclohexanone and i-butanol (a mixed solvent of xylylenemethylisobutylketone).
• Table 12 also shows the results of visual observation of the painted surface and the results of evaluating the initial adhesion and the aging adhesion according to Example 12.
• the epoxy resin solution of Example 12 was used by using the resole type phenol resin solution of Example 12 without converting the phenolic resin to butyrate. And then precondensed at 115 C for 4 hours. As confirmed by NMR after the precondensation, 85% of the methylol groups in the phenolic resin had been butyrylated.
• the coating film has a slight tendency to whiten.

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