JP2009072690A - Spray apparatus, method for forming coating film and coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a spray apparatus capable of forming a vinyl ester based coating film having excellent drying property and low odorous property in construction and excellent chemical resistance, strength and flexibility after being cured. <P>SOLUTION: The coating apparatus 10 is provided with a sprayer 11 for mixing a first raw material with a second raw material and spraying the mixture, a first supply hose 41 for supplying the first raw material to the sprayer 11, a second supply hose 42 for supplying the second raw material to the sprayer 11, a first hose heater 47 for heating the first supply hose 41, a second hose heater 48 for heating the second supply hose 42 and a hose temperature controller 44 for controlling the heating temperature of the first and the second hose heaters 47, 48 independently of each other. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a spray device, a method for manufacturing a coating film, and a coating film, and in particular, a spraying device used for forming a coating film made of a vinyl ester resin on an object such as an asphalt pavement. The present invention relates to a coating film manufacturing method and a coating film.

  Conventionally, a technique for forming a coating film of a polymer material on the surface of an object is known in order to impart functions such as durability and water repellency to an object such as an asphalt paved road or a concrete floor of a factory. .

  When the object to be constructed is required to have a drying property (speed of curing), chemical resistance, or the like, a vinyl ester resin is often used as a polymer material for forming a coating film.

  Conventionally, as a method for producing a coating film of a vinyl ester resin, a first raw material including a vinyl ester resin and a curing accelerator such as an amine, and a second raw material including a vinyl ester resin and a curing agent such as an organic peroxide are used. A method is known in which a curable resin composition is prepared by mixing in a spraying device, sprayed onto an object, and cured.

  In this method, the curing is started after the curing accelerator in the first raw material and the curing agent in the second raw material come into contact with each other in the spraying apparatus. Therefore, the curable resin composition prepared by mixing the first raw material and the second raw material in advance can be sprayed with a lower viscosity than when sprayed by supplying to the spraying device. Curing of the resin can be prevented.

  However, a curable resin composition containing a vinyl ester resin generally has a strong odor generated during spraying. For this reason, when a curable resin composition containing a vinyl ester resin is applied to an asphalt pavement road in a residential area, a concrete floor of a food factory, or the like, there is a problem that odor is emitted to the surroundings.

On the other hand, Patent Document 1 (Japanese Patent Application Laid-Open No. 2005-97523) discloses a curing property including a vinyl ester resin, a curing accelerator such as an amine, an accelerator such as a cobalt salt, and a curing agent such as an organic peroxide. A method of applying a resin composition to an object and curing it is disclosed. The coating film obtained by this method is excellent in dryness and low odor at the time of construction, and excellent in chemical resistance, strength and flexibility after curing.
JP 2005-97523 A

  However, Patent Document 1 applies a one-component type curable resin composition in which a vinyl ester resin, a curing accelerator such as an amine, an accelerator such as a cobalt salt, and a curing agent such as an organic peroxide are mixed. The method is only described, and a construction method for spraying with a sprayer using a two-component type material composed of a first material and a second material is not described.

  For this reason, when the curable resin composition disclosed in Patent Document 1 is applied as it is with a conventional spraying apparatus, the viscosity becomes high, spraying becomes difficult, and workability tends to deteriorate.

  That is, for convenience, the curable resin composition disclosed in Patent Document 1 is used as a first raw material containing a vinyl ester resin, a curing accelerator and an accelerator aid, and a second raw material containing a vinyl ester resin and a curing agent. In the case of separate installation, when a coating material such as titanium oxide is blended with either the first material or the second material, the viscosity of the one blended with the coating material increases, and the first material and the second material There is a risk that the properties of the cured product will be insufficient due to poor mixing with.

  In addition, the first raw material and the second raw material have a problem that curing is likely to proceed rapidly after being sufficiently mixed.

  That is, the first raw material and the second raw material prepared by dividing the curable resin composition disclosed in Patent Document 1 for convenience are difficult to mix, but the curing proceeds rapidly after mixing. Since it is easy to do, there existed a problem that the construction which sprays by dividing into 2 liquids is difficult.

  The present invention has been made in view of the above circumstances, and has a vinyl ester resin-based coating film excellent in chemical resistance, strength, and flexibility after curing, while being excellent in dryness and low odor during construction. It is an object of the present invention to provide a spray apparatus that can be produced, a method for producing a vinyl ester resin-based coating film using the spray apparatus, and a coating film produced by the production method.

  The spray device according to the present invention solves the above-described problems, and a sprayer that mixes and sprays the first raw material and the second raw material, and a first supply hose that supplies the first raw material to the sprayer. A second supply hose that supplies the second raw material to the sprayer, a first hose heater that heats the first supply hose, and a second hose heater that heats the second supply hose And a hose temperature controller capable of independently adjusting each of the heating temperatures of the first and second hose heaters.

  Moreover, the method for producing a coating film according to the present invention solves the above-described problems, and is a method for producing a coating film using the spray device, in which a first raw material and a second raw material are mixed. The curable resin composition obtained by spraying the object is sprayed to form an uncured coating film, and the coating film is a cured product of the curable resin composition by curing the uncured coating film. The first raw material contains a liquid vinyl ester resin, a tertiary amine and a reducing agent, and the second raw material contains a liquid vinyl ester resin and an organic peroxide. Features.

  Furthermore, the coating film according to the present invention solves the above-mentioned problems, and is characterized by being produced by the method for producing the coating film.

  According to the spray device and the method for producing a coating film according to the present invention, a vinyl ester resin-based coating that is excellent in dryness and low odor at the time of construction and excellent in chemical resistance, strength, and flexibility after curing. A film can be made.

  According to the coating film of the present invention, a coating film having excellent chemical resistance, strength, and flexibility can be obtained.

[Spraying device according to the present invention]
The spray device according to the present invention will be described with reference to the drawings. FIG. 1 is a view showing a spray system including a spray device according to the present invention.

(Spraying system)
As shown in FIG. 1, the spray system 1 includes an air compressor 61, a transfer pump 63, a first raw material container 64a, a second raw material container 64b, a raw material container heater 65, a raw material container temperature controller 66, The hydraulic pressure feeder 70, the solvent pump 76, and the spraying apparatus 10 are provided.

  The air compressor 61 is connected to the transfer pumps 63 and 63 via the air hoses 62a and 62b, and supplies air to the transfer pumps 63 and 63.

  The transfer pumps 63 and 63 are connected to the first raw material container 64a and the second raw material container 64b, respectively. The transfer pumps 63 and 63 hydraulically feed the first raw material and the second raw material from the first raw material container 64a and the second raw material container 64b through the raw material supply hose 67 using the air supplied from the air compressor 61 as a driving source. Supply to the vessel 70.

  The first raw material container 64a is charged with the first raw material, and the second raw material container 64b is charged with the second raw material.

  The first raw material container 64a and the second raw material container 64b are provided with raw material container heaters 65 and 65 for heating the first raw material or the second raw material, respectively. A raw material container temperature controller 66 for controlling the temperature of the raw material container heater 65 is connected to the raw material container heater 65.

  The hydraulic pressure feeder 70 includes a hydraulic motor 73 that supplies air. The upstream side of the hydraulic pressure feeder 70 is connected to the first raw material container 64 a and the second raw material container 64 b via the raw material supply hose 67, and the downstream side is connected to the supply hose assembly 40 of the spraying device 10.

  The hydraulic pressure feeder 70 supplies the first raw material and the second raw material transported from the first raw material container 64a and the second raw material container 64b by air to the supply hose assembly 40 of the spraying apparatus 10 at a predetermined flow rate, respectively. .

  The solvent pump 76 is connected to the supply hose assembly 40 of the spray device 10 via a solvent hose 77. The solvent pump 76 supplies the solvent for cleaning the supply hose assembly 40 and the sprayer 11 as necessary.

(Spraying device)
The spraying device 10 includes a sprayer 11, a first supply hose 41, a second supply hose 42, a first hose heater 47, a second hose heater 48, a hose temperature adjuster 44, and a temperature detection. And a container 50.

  The sprayer 11 is connected to the first supply hose 41 and the second supply hose 42 at the rear end. The sprayer 11 mixes the first raw material supplied from the first supply hose 41 and the second raw material supplied from the second supply hose 42 in the mixer unit 17 and sprays it from the nozzle unit 18.

  The first supply hose 41 is connected to the hydraulic pressure feeder 70 and the sprayer 11 and supplies the first raw material from the hydraulic pressure feeder 70 to the sprayer 11.

  The second supply hose 42 is connected to the hydraulic pressure feeder 70 and the sprayer 11, and supplies the second raw material from the hydraulic pressure feeder 70 to the sprayer 11.

  The first supply hose 41 is covered with a first hose heater 47 that heats the first supply hose 41 on the outer surface. The first hose heater 47 is made of an electrothermal material such as nichrome wire. The first hose heater 47 is connected to a hose temperature controller 44a for the first supply hose.

  The second supply hose 42 is covered with a second hose heater 48 whose outer surface heats the second supply hose 42. The second hose heater 48 is formed of an electrothermal material such as nichrome wire. The second hose heater 48 is connected to a hose temperature adjuster 44b for the second supply hose.

  Both the first supply hose 41 and the second supply hose 42 are coated with a coating agent such as vinyl chloride to form a supply hose assembly 40.

  The first supply hose 41 and the second supply hose 42 are connected to the hydraulic pressure feeder 70 via an insulating member 43a.

  The hose temperature controller 44 includes a hose temperature controller 44a for the first supply hose and a hose temperature controller 44b for the second supply hose.

  The hose temperature adjuster 44 a for the first supply hose is connected to the first hose heater 47 and adjusts the heating temperature of the first hose heater 47. The hose temperature controller 44 b for the second supply hose is connected to the second hose heater 48 and adjusts the heating temperature of the second hose heater 48.

  The hose temperature adjuster 44 can adjust the heating temperature of the first hose heater 47 and the heating temperature of the second hose heater 48 independently of each other.

  Based on the temperature of the first supply hose 41 and the temperature of the second supply hose 42 measured by the temperature detector 50, the hose temperature adjuster 44 determines the first hose heater 47 and the second hose heater 48. Each heating temperature can be adjusted independently.

  The supply hose assembly 40 is provided with a temperature detector 50 or an insulating member 43b in the middle. Adjacent supply hose assemblies 40, 40 are connected via a temperature detector 50 or an insulating member 43b.

  The temperature detector 50 detects the temperature of the first supply hose 41 and the temperature of the second supply hose 42, respectively. The detected temperature information is sent to the hose temperature adjuster 44 via a line (not shown).

  The insulating member 43b is provided in the supply hose assembly 40 between the temperature detector 50 and the sprayer 11, and the temperature detector 50 and the sprayer 11 are insulated.

  In the portion where the temperature detector 50 or the insulating member 43 b is provided, the hose heater cords 46, 46 housed in the supply hose assemblies 40, 40 are connected by a connector 49.

  The cord 46 for the hose heater is integrated with the cord portion other than the heating wire portion for heating the first supply hose 41 or the second supply hose 42 in the first hose heater 47 and the second hose heater 48. Is.

(Nebulizer)
The sprayer 11 will be described in detail with reference to the drawings. FIG. 2 is a front view of the sprayer 11. FIG. 3 is a plan view of the nebulizer 11. FIG. 4 is a partial cross-sectional view of FIG. 2 partially cut away in the AA direction.

  As shown in FIG. 2, the sprayer 11 includes a main body portion 12, a mixer portion 17, and a nozzle portion 18.

  The sprayer 11 is provided with a mixer portion 17 at a distal end portion on the downstream side of the main body portion 12, and a nozzle portion 18 is provided at a distal end portion on the downstream side of the mixer portion 17.

  The main body 12 includes a first body member 13, a second body member 14, a third body member 15, and a cap 16.

  The first body member 13, the second body member 14, and the third body member 15 are combined in the longitudinal direction to form one cylindrical main body 12.

  The first body member 13 is provided with a grip portion 19 that can be gripped by an operator.

  As shown in FIG. 4, a first supply hose 41 and a second supply hose 42 are connected to the rear end portion of the first body member 13.

  In the first body member 13, a first supply valve 21 connected to the first supply hose 41 and a second supply valve 22 connected to the second supply hose 42 are provided.

  The first body member 13 is provided with a valve operation portion 81 that adjusts the opening degree of each of the first supply valve 21 and the second supply valve 22.

  The valve operation portion 81 is provided on the curved surface portion of the columnar valve operation drum 82. In the center of the valve operation drum 82, shaft portions 83 and 84 for controlling the opening degree of the first supply valve 21 and the second supply valve 22 in conjunction with the rotation of the valve operation drum 82 are provided. The operator can control the opening degree of the first supply valve 21 and the second supply valve 22 by operating the valve operation unit 81.

  A first supply pipe 23 is connected to the downstream side of the first supply valve 21, and a second supply pipe 24 is connected to the downstream side of the second supply valve 22. The first supply pipe 23 and the second supply pipe 24 are provided such that the downstream end reaches the inside of the second body member 14.

  In the second body member 14, a joint 25 is provided on the downstream end face of the first supply pipe 23, and a joint 26 is provided on the downstream end face of the second supply pipe 24.

  A solvent supply pipe 56 that penetrates from the outside to the inside is provided on the side surface of the second body member 14. A solvent hose 77 is connected to the solvent supply pipe 56 on the upstream side via a solvent supply pipe 55, a joint 54, a solvent supply pipe 53, and a solvent supply valve 52. The solvent supply pipe 56 is provided with a joint 57 on the downstream side.

  At the downstream end of the second body member 14, a joint 25 of the first supply pipe 23, a joint 26 of the second supply pipe 24, and a joint 57 of the solvent supply pipe 56 are provided. The joint 25, the joint 26, and the joint 57 are arranged so as to be positioned at the apex of a substantially triangular shape when viewed from the mixer unit 17 side.

  The third body member 15 is connected to the second body member 14. The third body member 15 has a shape in which the downstream end 15a is narrowed down.

  In the third body member 15, the first bent pipe 27 is connected to the downstream side of the joint 25 of the first supply pipe 23, and the second bent pipe is connected to the downstream side of the joint 26 of the second supply pipe 24. 28 is connected, and the solvent bending pipe 58 is connected to the downstream side of the joint 57 of the solvent supply pipe 56. The first bent tube 27, the second bent tube 28, and the solvent bent tube 58 are made of copper.

  In the downstream end portion 15 a of the third body member, the first bent tube 27, the second bent tube 28, and the solvent bent tube 58 are bundled and covered with the seal portion 32. In the seal portion 32, the second portion 32b on the downstream side is thinner than the first portion 32a on the upstream side. The seal portion 32 is made of an elastic material such as rubber.

  FIG. 5 is a view showing an end face on the downstream side (mixer part 17 side) of the seal part 32. As shown in FIG. 5, the second portion 32 b on the downstream side of the seal portion 32 is narrowed so that the diameter is smaller than that of the first portion 32 a on the upstream side.

  The first bent tube 27, the second bent tube 28, and the solvent bent tube 58 open to the end face of the second portion 32b on the downstream side of the seal portion 32, and the first discharge port 29 and the second bent tube 58 respectively. A discharge port 30 and a solvent discharge port 59 are formed. The 1st discharge port 29, the 2nd discharge port 30, and the solvent discharge port 59 are arrange | positioned so that it may be located in the vertex of a substantially triangle.

  A cap 16 is attached to the outside of the downstream end portion 15a of the third body member. The cap 16 is formed with a tapered and open front end portion 16a on the downstream side. By attaching the cap 16 to the third body member, the seal portion 32 is fixed with the inner wall of the tip portion 16a of the cap contacting the outer surface of the seal portion 32.

  The mixer unit 17 is a cylindrical body, has a chamber 38 inside, and a static mixer 39 is provided in a part of the chamber 38 in the longitudinal direction. In the mixer portion 17, the second portion 32 b on the downstream side of the seal portion 32 is fitted into one end portion 17 a. A fitting portion 17b is provided around the end portion 17a of the mixer portion to be fitted to the tip end portion 16a of the cap.

  The static mixer 39 can sufficiently mix the first raw material and the second raw material discharged from the first discharge port 29 and the second discharge port 30 of the seal portion 32. The length of the static mixer 39 (symbol L in FIG. 4) is usually 20 cm to 35 cm.

  When the length of the static mixer 39 is within this range, the first raw material containing the vinyl ester resin, the curing accelerator and the accelerator aid can be sufficiently mixed with the second raw material containing the vinyl ester resin and the curing agent. In addition, spraying can be carried out satisfactorily without curing and the viscosity becoming too high.

  If the length of the static mixer 39 is less than 20 cm, the first raw material and the second raw material are likely to be insufficiently mixed. If the length of the static mixer 39 exceeds 35 cm, curing may start and spraying may be difficult. There is.

  The nozzle part 18 is provided in the front-end | tip part of the mixer part 17, and sprays the mixture of a 1st raw material and a 2nd raw material.

[Method for Manufacturing Coating Film According to the Present Invention]
Next, the manufacturing method of the coating film which concerns on this invention is demonstrated. In the method for producing a coating film according to the present invention, a specific first raw material and a specific second raw material are mixed by the spraying device 10 and sprayed onto an object, thereby producing a coating film on the surface of the object. Is the method.

  In the present invention, the curable resin composition obtained by mixing the first raw material and the second raw material is cured to form a cured product. When the curable resin composition is sprayed onto an object such as an asphalt pavement surface or a concrete surface, a coating film made of a cured product of the curable resin composition is formed on the surface of the object.

(First raw material)
The first raw material used in the present invention contains a liquid vinyl ester resin, a tertiary amine and a reducing agent.

(Liquid vinyl ester resin)
The vinyl ester resin used in the present invention is a mixture of a liquid vinyl ester (A) and a polymerizable unsaturated monomer (B).

(Liquid vinyl ester (A))
The liquid vinyl ester (A) used in the present invention is obtained by reacting an epoxy resin with a saturated monobasic acid, a polybasic acid and an unsaturated monobasic acid.

(Epoxy resin)
As the epoxy resin used in the present invention, bisphenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, aralkyl diphenol type epoxy resin, diglycidyl type epoxy resin, alicyclic type epoxy resin, oxazolidone ring-containing epoxy resin, A novolac type epoxy resin, a trisphenol methane type epoxy resin, etc. are mentioned.

  Examples of the bisphenol type epoxy resin include an epoxy resin obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin and / or methyl epichlorohydrin, glycidyl ether of bisphenol A and the above-mentioned Examples thereof include epoxy resins obtained by reacting a condensate of bisphenols with epichlorohydrin and / or methyl epichlorohydrin.

  Examples of the biphenyl type epoxy resin include an epoxy resin obtained by reacting biphenol with epichlorohydrin and / or methyl epichlorohydrin.

  Examples of naphthalene type epoxy resins include epoxy resins obtained by reacting dihydroxynaphthalene with epichlorohydrin and / or methyl epichlorohydrin.

  Examples of the aralkyl diphenol type epoxy resin include an epoxy resin obtained by reacting aralkyl phenol with epichlorohydrin and / or methyl epichlorohydrin.

  Examples of the diglycidyl type epoxy resin include dimer acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester.

  Examples of the alicyclic epoxy resin include alicyclic diepoxy acetal, alicyclic diepoxy adipate, and alicyclic diepoxycarboxylate.

  As the oxazolidone ring-containing epoxy resin, epoxy resins such as the above bisphenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, aralkyl diphenol type epoxy resin, diglycidyl type epoxy resin, alicyclic type epoxy resin, and diisocyanate An epoxy resin obtained by reacting is used. Examples of the oxazolidone ring-containing epoxy resin include Araldite AER4152 made by Asahi Kasei Epoxy.

  Examples of the novolak type epoxy resin include an epoxy resin obtained by reacting phenol novolak or cresol novolak with epichlorohydrin and / or methyl epichlorohydrin.

  Examples of the trisphenol methane type epoxy resin include an epoxy resin obtained by reacting trisphenol methane or tris-resole methane with epichlorohydrin and / or methyl epichlorohydrin.

(Saturated monobasic acid)
Examples of the saturated monobasic acid used in the present invention include known monobasic acids such as monobasic carboxylic acids having an alkyl chain such as acetic acid, propionic acid, butanoic acid and octylic acid; benzoic acid, α-toluic acid, Aromatic monobasic carboxylic acids such as salicylic acid; cycloaliphatic carboxylic acids such as cyclohexane carboxylic acid, cyclopropane carboxylic acid, cycloheptane carboxylic acid; 2-furan carboxylic acid, tetrahydrofuran carboxylic acid, 3,4-dihydro-2H- Examples thereof include monobasic carboxylic acids having a heterocycle such as pyran-6-carboxylic acid.

  Of these saturated monobasic acids, 2-furancarboxylic acid is preferred because of its high drying properties.

  In the present invention, the amount of saturated monobasic acid added to the epoxy group is 20 equivalent% or less, and the amount of unsaturated monobasic acid and polybasic acid added to the remaining epoxy group is unsaturated monobasic acid: When the ratio of the equivalent amount of the basic acid is within the range of 90 to 10:10 to 90, a plurality of types of saturated monobasic acids can be used in combination.

(Polybasic acid)
The polybasic acid used in the present invention is used to increase the molecular weight of the epoxy resin.

  As the polybasic acid used in the present invention, known ones can be used. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, Hexahydrophthalic acid, dimer acid, dimer acid hydride (hydrogenated dimer acid), ethylene glycol / 2 mol maleic anhydride adduct, polyethylene glycol / 2 mol maleic anhydride adduct, propylene glycol / 2 mol maleic anhydride Adduct, Polypropylene glycol 2 mol maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16- (6-ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid Acid, carboxyl group-terminated butadiene / acrylonitrile copolymer (quotient Name Hycar CTBN), and the like.

  Among these polybasic acids, dimer acid is preferable because the elongation percentage of the cured product of the curable resin composition applied to an object and dried is increased.

  As the dimer acid, any of an aliphatic type, a monocyclic type, a multicyclic type, and a hydride can be used. The dimer acid may be a mixture containing monomers, trimers, tetramers and the like.

  Specific examples of the dimer acid include Hari dimer 270S manufactured by Harima Kasei Co., Ltd., ULB-20 manufactured by Okamura Oil Co., Ltd., Enpole 1061 manufactured by Cognis Japan Co., Ltd., and Empol 1008.

(Unsaturated monobasic acid)
Examples of the unsaturated monobasic acid used in the present invention include known ones such as (meth) acrylic acid, crotonic acid, cinnamic acid, a compound having one hydroxyl group and one or more (meth) acryloyl groups. And a reaction product of polybasic acid anhydride.

  The liquid vinyl ester (A) used in the present invention is obtained by reacting the above epoxy resin with a saturated monobasic acid, polybasic acid and unsaturated monobasic acid. The liquid vinyl ester (A) is preferably one obtained by reacting an epoxy resin with a saturated monobasic acid, a polybasic acid and an unsaturated monobasic acid in this order.

  The liquid vinyl ester (A) used in the present invention is obtained by adding a saturated monobasic acid to 20% or less, preferably 0.1 to 19% of the number of epoxy groups of the epoxy resin. When the addition ratio of the saturated monobasic acid is within the above range, sufficient unsaturated groups are present in the vinyl ester skeleton, and a cured product having good physical properties can be obtained.

  In the liquid vinyl ester (A) used in the present invention, the equivalent ratio of unsaturated monobasic acid: polybasic acid added to the remaining epoxy group is usually 90:10 to 10:90, preferably 80:20 to 20:80. When the equivalent ratio of unsaturated monobasic acid: polybasic acid is within the above range, a cured product having a balance between flexibility and strength can be obtained.

(Polymerizable unsaturated monomer (B))
The polymerizable unsaturated monomer (B) used in the present invention is blended with the liquid vinyl ester (A) in order to lower the viscosity of the resin and improve the hardness, strength, chemical resistance, water resistance and the like.

  Examples of the polymerizable unsaturated monomer (B) used in the present invention include styrene; alkyl derivatives at the α-, o-, m- and p-positions of styrene, nitro derivatives, cyano derivatives, amide derivatives and ester derivatives; And styrene monomers such as chlorostyrene, vinyltoluene and divinylbenzene; and (meth) acrylate monomers.

  Of these polymerizable unsaturated monomers (B), (meth) acrylate monomers are preferred because they have less odor and little influence on other environments.

  Examples of (meth) acrylate monomers include ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl. (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-methacryloyloxy Ethyl 2-hydroxypropyl phthalate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, trifluoroethyl (meth) Examples include acrylate, perfluorooctylethyl (meth) acrylate, allyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.

  Among these (meth) acrylate monomers, dicyclopentenyloxyethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferable because they have less odor, high drying properties, and excellent physical properties such as elongation. .

  The polymerizable unsaturated monomer (B) can be used alone or in combination.

  In the polymerizable unsaturated monomer (B) used in the present invention, a (meth) acrylic acid ester compound having two or more (meth) acryloyl groups in the molecule may be used in combination with the above monomer.

As the (meth) acrylic acid ester compound having two or more (meth) acryloyl groups in the molecule, known compounds can be used, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, trimethylolpropane tri Meth) compound represented by the acrylate of various glycols (meth) acrylic acid ester or the following general formula (1), and the like.

  Examples of the compound represented by the general formula (1) include 2,2-bis [4- (methacryloxyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .: BPE-100), 2,2-bis [ 4- (methacryloxy / diethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .: BPE-200), 2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .: BPE) -500), 2,2-bis [4- (acryloxydiethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-BPE-4), 2,2-bis [4- (acryloxypolyethoxy) phenyl ] Propane (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-BPE-10) and the like.

  The vinyl ester resin used in the present invention is a mixture of the liquid vinyl ester (A) and the polymerizable unsaturated monomer (B). As the vinyl ester resin, one obtained by dissolving a liquid vinyl ester (A) in a polymerizable unsaturated monomer (B) is usually used.

  In the vinyl ester resin, the polymerizable unsaturated monomer (B) is usually 10 to 250 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the vinyl ester. When the blending amount of the polymerizable unsaturated monomer (B) is 10 parts by weight or more, the cured product has an appropriate viscosity, workability, wettability to fibers and aggregates, wettability and penetration into the adherend. Property is improved. When the blending amount of the polymerizable unsaturated monomer (B) is 250 parts by weight or less, the cured product has sufficient hardness, and chemical resistance, water resistance, and the like are improved.

(Oxidized polymer group-containing polymer (C))
The vinyl ester resin used in the present invention is an oxidative polymerization having an allyl ether group (allyloxy group) or a benzyl ether group (benzyloxy group) in addition to the vinyl ester (A) and the polymerizable unsaturated monomer (B). The group-containing polymer (C) may be included.

  The oxidatively polymerizable group-containing polymer (C) is a polymer having a functional group that performs oxidative polymerization (air curing), greatly improving the drying property of the curable resin composition, and uniforming the finish of the coating film and molding surface. Has the effect of Here, oxidative polymerization (air curing) refers to, for example, allyl ether groups (allyloxy groups) and the like, which are crosslinks associated with the generation and decomposition of peroxides by oxidation of methylene bonds between ether bonds and double bonds. Point to.

  Examples of the oxidative polymerization (air-curing) group contained in the oxidative polymerization group-containing polymer (C) include those having an allyl group and a benzyl group. Those having an ether group (benzyloxy group) are preferred.

  The oxidative polymerization group-containing polymer (C) may be a polymer obtained by polymerizing a monomer containing an oxidative polymerization group, or may be a polymer obtained by introducing an oxidative polymerization group into the polymer.

  Examples of the monomer containing an oxidative polymerization group include unsaturated compounds having an allyl ether group (allyloxy group) or a benzyl ether group (benzyloxy group). Specific examples of the monomer containing an oxidative polymerization group include allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl ether, vinyl benzyl- (2-ethylhexyl) ether, vinyl benzyl (β-methoxymethyl) ether, Vinyl benzyl (n-butoxypropyl) ether, vinyl benzyl cyclohexyl ether, vinyl benzyl- (β-phenoxyethyl) ether, vinyl benzyl dicyclopentenyl ether, vinyl benzyl dicyclopentenyl oxyethyl ether, vinyl benzyl dicyclopentenyl methyl ether, Divinyl benzyl ether is mentioned.

  When the oxidatively polymerizable group-containing polymer (C) is polymerized by adding a monomer such as dicyclopentenyl (meth) acrylate or dicyclopentenyloxyethyl (meth) acrylate to the above monomer, the curable resin composition is dried. Can be improved.

  In addition, the method for producing an oxidative polymerization group-containing polymer (C) by introducing an oxidative polymerization group into the polymer is not particularly limited. For example, a polymer having an epoxy group, a carboxyl group, and an allyl ether group (allyloxy group) And a method of reacting a polymer having a carboxyl group and / or an amino group with a compound having an epoxy group and an allyl ether group (allyloxy group).

  Specific examples of the compound having an epoxy group and an allyl ether group (allyloxy group) include allyl glycidyl ether and 2,6-diglycidyl phenyl allyl ether. Specific examples of the compound having a carboxyl group and an allyl ether group (allyloxy group) include those obtained by adding an acid anhydride to a compound having a hydroxyl group and an allyl ether group (allyloxy group).

  The polymer having an epoxy group, a carboxyl group, or an amino group may be a commercially available product or a synthesized product. Specific examples of commercially available products include Modiper A4200, Modiper A4100, Blemmer CP-30, Blemmer CP-50M (Nippon Yushi Co., Ltd.), ZEON F301 (Nippon Zeon Corporation), and the like. When synthesizing a polymer having an epoxy group, a carboxyl group, or an amino group, for example, a (meth) acrylate monomer composition containing at least a (meth) acrylate monomer having each functional group is copolymerized. The polymerization method may be solution polymerization or emulsion polymerization.

  In the vinyl ester resin, the oxidatively polymerizable group-containing polymer (C) is usually blended in an amount of 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the vinyl ester. When the blending amount of the oxidative polymerization group-containing polymer (C) is 0.01 parts by weight or more, the effect of improving the drying property of the curable resin composition is exhibited, and when it is 50 parts by weight or less, the resin viscosity is moderate. The workability of spraying the curable resin composition and the drying property of the curable resin composition are improved.

  The 1st raw material used by this invention contains a tertiary amine and a reducing agent in addition to said liquid vinyl ester resin.

(Tertiary amine)
The tertiary amine used in the present invention is a curing accelerator, and performs normal temperature radical polymerization by contacting with an organic peroxide that is a curing agent, thereby substantially starting curing of the curable resin composition. .

  Examples of the tertiary amine used in the present invention include aromatic tertiary amines.

  Examples of the aromatic tertiary amine used in the present invention include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N-methyl-N-β-hydroxyethylaniline, N -Butyl-N-β-hydroxyethylaniline, N-methyl-N-β-hydroxyethyl-p-toluidine, N-butyl-N-β-hydroxyethyl-p-toluidine, N-methyl-N-β-hydroxy Propylaniline, N-methyl-N-β-hydroxypropyl-p-toluidine, N, N-di (β-hydroxyethyl) aniline, N, N-di (β-hydroxypropyl) aniline, N, N-di ( β-hydroxyethyl) -p-toluidine, N, N-di (β-hydroxypropyl) -p-toluidine, N, N-diisopropylol-p-toluidine And the like.

  Among these aromatic tertiary amines, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine, N, N-di (β- Hydroxypropyl) -p-toluidine and N, N-diisopropylol-p-toluidine are preferable because they have good curability (dryability), that is, fast curing. Aromatic tertiary amines can be used alone or in combination.

  The aromatic tertiary amine is usually added in an amount of 0.1 to 5 parts by weight, preferably 1 to 2 parts by weight, per 100 parts by weight of the vinyl ester resin. When the amount of the aromatic tertiary amine is within the above range, the pot life is preferably an appropriate length.

(Reducing agent)
The reducing agent used in the present invention functions as an acceleration aid and accelerates the curing reaction of the curable resin composition.

  Examples of the reducing agent used in the present invention include cobalt salts such as cobalt octylate and cobalt naphthenate, and vanadium compounds such as vanadium pentoxide. Among these, the use of cobalt salts is preferable because the pot life becomes longer.

  When the reducing agent is a cobalt salt, the reducing agent is usually 0.1 to 5 parts by weight with respect to 100 parts by weight of the vinyl ester resin, in terms of the amount of cobalt converted to about 5 to 10%. It is preferable to blend 0.005 to 1 part by weight in terms of metal. When the blending amount is in the range of 0.1 to 5 parts by weight, the oxidative polymerization rate is moderate and it is difficult to adversely affect the curing.

  Further, when the reducing agent is a cobalt salt, the amount of the reducing agent is usually 10: 1 to 1 by weight ratio (organic peroxide: cobalt salt) between the organic peroxide and the reducing agent cobalt salt. 1:10.

(Second raw material)
The second raw material used in the present invention contains a liquid vinyl ester resin and an organic peroxide. Since the liquid vinyl ester resin used for the second raw material is the same as the vinyl ester resin used for the first raw material, description thereof is omitted.

(Organic peroxide)
The organic peroxide used in the present invention is a curing agent, and performs normal temperature radical polymerization by contacting with a tertiary amine that is a curing accelerator, thereby substantially starting curing of the curable resin composition. .

  Examples of the organic peroxide used in the present invention include ketone peroxide, peroxyketal, hydroperoxide, diallyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, and azo compound.

  Specific examples of the organic peroxide include benzoyl peroxide (benzoyl peroxide), dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 1,1-bis (t -Butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 3-isopropyl hydroperoxide, t-butyl hydroperoxide , Dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoylper Oxide, LA Lil peroxide, azobisisobutyronitrile, an azo bis-carboxamido. Of these, benzoyl peroxide is preferred because of its high reactivity.

  In the second raw material, the organic peroxide is usually blended in an amount of 2 to 10 parts by weight, preferably 3 to 7 parts by weight with respect to 100 parts by weight of the vinyl ester resin. When the blending amount of the organic peroxide is within the above range, curing proceeds sufficiently and the physical properties of the cured product are improved.

(Wax (D))
In the present invention, wax (D) may be further blended in at least one of the first raw material and the second raw material in order to block air from the coating surface.

  Examples of the waxes (D) used in the present invention include known waxes such as petroleum waxes such as paraffin wax and microcrystalline; plant waxes such as candelilla wax, rice wax and wood wax; beeswax and spermaceti Animal waxes such as; mineral waxes such as montan wax; synthetic waxes such as polyethylene wax and amide wax; special products such as BYK-S-750, BYK-S-740, BYK-LP-S6665 (manufactured by BYK-Chemie) A wax is mentioned.

  These waxes (D) can be used alone or in combination.

  When the waxes (D) are blended in the first raw material, the second raw material, etc., the waxes (D) are usually 0 with respect to 100 parts by weight of the total vinyl ester resin contained in the first raw material and the second raw material. 0.05 to 5.0 parts by weight are blended. A solvent or the like may be used in combination with at least one of the first raw material and the second raw material in order to more effectively utilize the action of blocking air from the wax coating surface. Examples of the solvent used in combination include n-dodecane.

(Photopolymerization initiator)
In the present invention, a photopolymerization initiator may be further blended in at least one of the first raw material and the second raw material.

  Examples of the photopolymerization initiator used in the present invention include those having photosensitivity in either the ultraviolet or near infrared region.

  As the ultraviolet polymerization initiator, known polymerization initiators such as acetophenone, benzyl ketal, and (bis) acylphosphine oxide are used.

  An initiator having photosensitivity from the ultraviolet light region to the visible light region is effective for enhancing light transmittance. As the initiator having photosensitivity from the ultraviolet light to the visible light region, an ultraviolet polymerization initiator such as (bis) acylphosphine oxide is preferable.

  Specific examples of the photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure-819, manufactured by Ciba Specialty Chemicals), 2,4,6-trimethyl. Benzoyl-diphenylphosphine oxide (trade name Lucirin TPO, manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) A trade name Darocur 4265 in which 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name Lucirin TPO, manufactured by BASF Corporation) is mixed at a ratio of 50% / 50% can be mentioned.

  Among the photopolymerization initiators, the visible light polymerization initiator may be any photopolymerization initiator having photosensitivity in a wavelength range of 380 nm to 780 nm (visible light region), and may be used in combination.

  As a visible light polymerization initiator having photosensitivity in the visible light region, for example, Yamaoka et al., “Surface”, 27 (7), 548 (1989), Sato et al., “Summary of 3rd Polymer Material Forum”, IBP18 ( 1994), a single visible light polymerization initiator such as camphorquinone, benzyltrimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, dicyclopentadienyltitanium-di (pentafluorophenyl), organic peroxide / Hexaary described in JP-B-45-37377, such as a dye system, diphenyliodonium salt / dye, imidazole / keto compound, hexaarylbiimidazole compound / hydrogen donating compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye Rubyimidazole / Radika Known combined initiator systems, such as generating agents.

  Examples of the photopolymerization initiator having photosensitivity in the visible light or near infrared light region having a wavelength of 500 nm or longer include a combination of an organic boron compound and a cationic dye. By combining this organoboron compound with a cationic dye having a photosensitive wavelength in the visible light or near infrared light region, the dye that has been irradiated with light having a wavelength in the photosensitive region is excited to exchange electrons with the organoboron compound. As the dye disappears, radicals are generated and a coexisting polymerizable unsaturated compound undergoes a polymerization reaction. In this polymerization reaction, unlike the conventional ultraviolet polymerization reaction, the generated radicals can be easily controlled, and can be easily stopped when a part of the unsaturated group in the resin is radically polymerized. In addition, since a long wavelength in the visible light or near-infrared light region is used, the reaction can easily proceed even in a system to which a filler or pigment is added.

  Examples of initiators having photosensitivity in either the ultraviolet or near-infrared region are those disclosed in JP-A-2000-297127 and JP-A-2001-139543. There are detailed descriptions in the Gazette.

  A photoinitiator is 0.01-15 weight part normally with respect to 100 weight part of vinyl ester resin, Preferably 0.05-10 weight part is mix | blended. When the blending amount of the photopolymerization initiator is in the range of 0.01 to 15 parts by weight, the polymerization proceeds sufficiently and a cured product having good physical properties is obtained.

  When the organic peroxide and the photopolymerization initiator are used in combination, the total amount of the organic peroxide and the photopolymerization initiator is usually 0.02 to 30 parts by weight, preferably 0.00. 1 to 20 parts by weight is blended.

  Moreover, when using together an organic peroxide and a photoinitiator, the weight ratio (organic peroxide / photoinitiator) of an organic peroxide and a photoinitiator is 5 / 0.1-0. 1/5, preferably 1 / 0.1 to 0.1 / 1.

(Raw material for paint)
At least one of the first raw material and the second raw material may further include a coating material. Examples of the coating material used in the present invention include pigments such as titanium oxide and infrared reflective pigments such as Cr ₂ O ₃ , CuCr ₂ O ₄ , (Co, Fe) (Fe, Cr) ₂ O _4. .

  When the paint raw material is blended in both the first raw material and the second raw material, it is usually 10 to 50 parts by weight, preferably 20 to 25 parts by weight based on 100 parts by weight of the total amount of the first raw material and the second raw material. Blended.

  Further, when the coating material is blended with either the first raw material or the second raw material, it is usually 20 to 100 parts by weight, preferably 40 to 50 parts by weight with respect to 100 parts by weight of the first raw material or the second raw material. Blended.

  Next, the manufacturing method of the coating film according to the present invention will be described more specifically.

  In the method for producing a coating film according to the present invention, the first raw material and the second raw material are mixed by the sprayer 11 of the spraying device 10, sprayed onto the object, cured, and coated on the surface of the object. A film is formed.

(Raw material viscosity adjustment process)
First, by adjusting the temperature of the first raw material and the second raw material in the first raw material container 64a and the second raw material container 64b using the raw material container heater 65 and the raw material container temperature controller 66 as the raw material viscosity adjusting step. The viscosity of the first raw material and the second raw material is adjusted.

  Further, the first hose heater 47, the second hose heater 48, and the hose temperature adjuster 44 are used when the first raw material and the second raw material are supplied into the first supply hose 41 and the second supply hose 42, respectively. In addition, preparation is made so that the temperature of the first raw material and the second raw material can be adjusted.

  When the first raw material and the second raw material are mixed in the mixer section 17 of the sprayer 11, the respective viscosities are usually 0.3 to 2.0 Pa · s, preferably 0.5 to 1.2 Pa · s. To do. When the viscosity is within the above range, the first raw material and the second raw material are sufficiently mixed, and the curable resin composition obtained by mixing has a viscosity suitable for spraying.

  The difference in viscosity between the first raw material and the second raw material occurs, for example, when the paint raw material is blended only in one of the first raw material and the second raw material, or when a large amount of the paint raw material is blended in one. For example, since the coating material is often blended with the second material, the viscosity of the second material is likely to be higher than that of the first material.

  In addition, when the first raw material and the second raw material are mixed in the mixer section 17 of the sprayer 11, the difference in viscosity between the first raw material and the second raw material is usually within 1.0 Pa · s, preferably 0.5 Pa.・ Set it within s.

  Examples of the method for setting the difference in viscosity between the first raw material and the second raw material within the above range include a method in which a high viscosity raw material is heated to a higher temperature than a low viscosity raw material.

  The viscosity of the first raw material and the second raw material is adjusted by adjusting the temperature of the first raw material and the second raw material. The temperature control of the first material and the second material is performed by using, for example, the first hose heater 47, the second hose heater 48, the hose temperature controller 44, the material container heater 65, the material container temperature controller 66, and the like. .

(Spraying process)
After the raw material viscosity adjusting step, as a spraying step, a curable resin composition obtained by mixing the first raw material and the second raw material is sprayed from the sprayer 11 onto the target object, and an uncured coating film is applied to the surface of the target object. Form.

  Specifically, first, the first supply valve 21 and the second supply valve 21 and the second supply valve 21 are operated by gripping the grip portion 19 of the sprayer 11, directing the nozzle portion 18 toward the surface of the object, and operating the valve operation portion 81 in an unillustrated opening direction. Are simultaneously opened.

  By simultaneously opening the first supply valve 21 and the second supply valve 22, the first raw material and the second raw material are transferred from the first raw material container 64a and the second raw material container 64b to the transfer pump 63 and the hydraulic pressure feeder 70. Thus, a constant amount is supplied into the sprayer 11 via the first supply hose 41 and the second supply hose 42.

  Next, the first raw material and the second raw material supplied into the sprayer 11 are supplied to the mixer unit 17 from the first outlet 29 and the second outlet 30 of the main body 12, and the static in the mixer 17 is obtained. A curable resin composition is prepared by mixing with a mixer 39.

  Further, the curable resin composition produced in the mixer unit 17 is injected from the nozzle unit 18 into a desired shape, for example, in a fan shape, a conical shape, or the like.

  The curable resin composition sprayed on the surface of the object is not cured for a predetermined time after being sprayed, and is an uncured coating film.

  Examples of the object used in the present invention include an asphalt pavement surface and a concrete surface.

  When ending the spraying process, the valve operating portion 81 is operated in a closing direction (not shown) to simultaneously close the first supply valve 21 and the second supply valve 22, and the first raw material and the second feed to the mixer portion 17 are closed. Stop supplying raw materials.

  After the spraying process is completed, the solvent supply valve 52 is opened if necessary, and a cleaning fluid such as a solvent is fed into the chamber 38 of the mixer unit 17 at a predetermined pressure, and the chamber 38 is cleaned, thereby Prevention of sticking of the raw material, the second raw material or the curable resin composition.

  When spraying a curable resin composition on the surface of an object, the surface of the object is ground-treated before applying the curable resin composition, or a primer is applied to the surface of the ground-treated object. Thus, it is preferable to improve the fixability of the curable resin composition to the surface of the object.

(Curing process)
After the spraying step, as the curing step, the uncured coating film is cured to form a coating film that is a cured product of the curable resin composition on the surface of the object.

  Specifically, the curable resin composition sprayed on the surface of the object is dried and cured by room temperature curing, photocuring, or a method using a combination of photocuring and room temperature curing to form a coating film. It is preferable to use photocuring or a method of using both photocuring and room temperature curing since it can be dried and cured in a short time.

  As a light source in the case of performing photocuring or photocuring combined room temperature curing, any light source having a spectral distribution in the photosensitive wavelength region of the photopolymerization initiator may be used. For example, a near-infrared lamp, a sodium lamp, a halogen lamp, a fluorescent lamp , Metal halide lamps, mercury lamps, high-pressure mercury lamps, and sunlight are used. Among these light sources, from the viewpoint of safety at the work site, a light source of visible light to near infrared light is preferable. Here, visible light refers to light in the wavelength region of 380 to 780 nm, and near infrared light refers to light in the wavelength region of 780 to 1200 nm. Moreover, ultraviolet light refers to the light ray of a wavelength range of 280 to 380 nm.

  The coating film formed on the surface of the object is excellent in chemical resistance, strength and flexibility.

  When the target object is an asphalt pavement surface, the coating film formed on the surface of the target object can be used for non-slip pavement, drainage pavement and the like of the asphalt pavement surface. Moreover, the coating film formed on the surface of the object can be used for applications such as primer, lining, top coat, floor slab (concrete slab) waterproofing when the object is a concrete surface.

  In the present invention, anti-slip properties may be imparted to the coating film by embedding an anti-slip bone material in the coating film. As a method of embedding the anti-slip aggregate in the coating film, for example, there is a method of performing the following aggregate spraying step, second spraying step and second curing step on the uncured coating film obtained in the spraying step. Can be mentioned. Hereinafter, the spraying process is also referred to as a first spraying process, and the curing process is also referred to as a first curing process.

(Aggregate application process)
After the spraying step (first spraying step), in the aggregate spraying step, the anti-slip aggregate is sprayed on the surface of the uncured coating, and at least a part of the anti-slip aggregate is embedded in the aggregate embedded uncured coating Form. Here, that at least a part of the anti-slip aggregate is embedded means that at least a part of the anti-slip aggregate particles are embedded in the uncured coating film.

Examples of the anti-slip aggregate used in the present invention include those having a spinel (MgO.Al ₂ O ₃ ) type structure, those having a crystal structure of forsterite (2MgO · SiO ₂ ), silica sand (SiO ₂ ), and alumina. (Al ₂ O ₃ ) and the like.

  The particle size of the anti-slip aggregate is usually 0.1 mm to 40 mm, preferably 0.1 mm to 20 mm. If the particle size of the anti-slip aggregate exceeds 40 mm, the anti-slip effect becomes too high, which may cause discomfort during walking and early wear of the vehicle tire. When the particle size of the anti-slip aggregate is less than 0.1 mm, it is difficult to obtain a sufficient anti-slip effect.

  As a method of spraying the anti-slip aggregate, a known method such as spraying by a machine or human power can be used. When there is an excess anti-slip bone material on the surface of the aggregate embedded uncured coating, it is preferable to remove the anti-slip bone material with a broom or the like because the variation in the thickness of the coating film is reduced.

  The application amount of the anti-slip aggregate is usually 10% to 90% by weight, preferably 30% to 70% by weight, based on the total weight of the coating film including the anti-slip aggregate.

If the application amount is less than 10% by weight, the anti-slip effect may be reduced, and if it exceeds 90% by weight, the durability of the coating film may not be sufficient.

(Second spraying step)
In the second spraying step after the aggregate spraying step, the curable resin composition is further sprayed on the surface of the aggregate embedded uncured coating to form an aggregate-containing uncured coating containing the anti-slip aggregate. .

  Since the spraying operation of the curable resin composition in the second spraying step is the same as the spraying step (first spraying step), description thereof is omitted.

  When this process is performed, the sprayed anti-slip aggregate is firmly fixed to the coating film, and the anti-slip property of the coating film is easily maintained over a long period of time, which is preferable.

(Second curing step)
After the second spraying step, in the second curing step, the aggregate-containing uncured coating film is cured to form a coating film that is a cured product of the curable resin composition containing the anti-slip aggregate.

  Since the curing operation in the second curing step is the same as the above-described curing step (first curing step), description thereof is omitted.

  If this process is performed, the coating film which includes a non-slip | skid aggregate on the surface of a target object can be formed.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is limited to these Examples and is not interpreted.

  In the examples, “parts” and “%” are based on weight, and “equivalent” indicates the equivalent of each component relating to the reaction between the epoxy and the acid.

[Synthesis Example 1] (Vinyl ester resin: VE-1)
In a container equipped with a stirrer, thermometer, and gas introduction tube, 567 g (3.0 equivalents) of Araldite AER2603 (epoxy resin manufactured by Asahi Kasei Kogyo Co., Ltd.) having an epoxy equivalent of 189 obtained by the reaction of bisphenol A and epichlorohydrin is 22 g of octylic acid (3.0 equivalents). 0.15 equivalent), 116 g (1.35 equivalent) of methacrylic acid, 435 g (1.5 equivalent) of Halidimer 270S (Harima Chemical Co., Ltd. dimer acid), 2.5 g of triethylamine, 0.25 g of methylhydroquinone, and air Was allowed to react for 4 hours at 120 ° C., and the reaction was terminated when the acid value reached 5 mgKOH / g. To the vinyl ester (A) thus obtained, 1825 g of dicyclopentenyl methacrylate (trade name: QM-57T, manufactured by Rohm and Haas Co., Ltd.), which is a polymerizable unsaturated monomer (B), was added, and a vinyl ester resin ( VE-1) was obtained.

[Example 1] (Construction of curable resin composition-1 on asphalt pavement)
(Preparation of the first raw material-1)
For 100 g of the vinyl ester resin VE-1 obtained in Synthesis Example 1, 1.0 g of 125F paraffin wax (manufactured by Nippon Seiwa), and JR-1000 (made by Teika Co., Ltd., rutile titanium oxide) as a white pigment 7.0 g AA-200 Blue (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 3.0 g as a blue pigment, AR-300 brown (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 0.2 g as a brown pigment, AY-150 yellow as a yellow pigment (Infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 0.2 g, AG-235 black (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 3.0 g as a black pigment, N, N-di (β-hydroxyethyl) -p-toluidine (Morin Chemical Co., Ltd. PT-2HE) 1.5g and 8% cobalt octylate 2.0g were added, and the 1st raw material-1 was prepared.

(Preparation of second raw material-1)
For 100 g of the vinyl ester resin VE-1 obtained in Synthesis Example 1, 1.0 g of 125F paraffin wax (manufactured by Nippon Seiwa), and JR-1000 (made by Teika Co., Ltd., rutile titanium oxide) as a white pigment 7.0 g AA-200 Blue (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 3.0 g as a blue pigment, AR-300 brown (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 0.2 g as a brown pigment, AY-150 yellow as a yellow pigment (Infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 0.2 g, AG-235 black (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 3.0 g, 40% purity benzoyl peroxide (NIPPER NS 4.0g was added and the 2nd raw material-1 was prepared.

(Spraying of curable resin composition-1)
A spray test was performed using the spray device 10 including the sprayer 11 shown in FIGS. In the sprayer 11, the length of the static mixer 39 was 20 cm.

  The first raw material-1 made 0.6 Pa · s at 40 ° C. and the second raw material-1 made 0.6 Pa · s at 40 ° C. are supplied to the spraying device 10 6.0 l / min at a time. The curable resin composition-1 that is a mixture of -1 and the second raw material-1 was sprayed from the nozzle part 18 onto the asphalt pavement surface that is the object. Spraying could be done well.

Before the curable resin composition-1 on the surface of the asphalt pavement is cured, 1.0 kg of a non-slip aggregate having an average particle size of 1.0 mm (trade name Neo Emery, manufactured by Okazaki Huttenus Albertus Kasei Co., Ltd.) / M ^{2 was} sprayed, and curable resin composition-1 was further sprayed thereon. The curable resin composition-1 was sprayed so that the anti-slip aggregate was not exposed.

  When spraying at room temperature after spraying, a coating film having a uniform composition and a thickness of 1.5 mm was formed on the asphalt pavement. The content of the anti-slip aggregate in the coating film was 56% by weight.

(Measurement of wear resistance)
About the asphalt pavement which has a coating film, the abrasion resistance of the coating film was measured by the simple rotation labeling test.

  The method of the simple rotation labeling test is as follows. That is, first, an asphalt pavement having a coating film was cut to prepare a specimen having a length of 300 mm × width of 300 mm × thickness of 50 mm. Next, after placing the specimen on a turntable with the coating film facing upward, an automobile tire having a ladder metal chain wound around the tread was placed on the surface of the coating film. The wheel load of the automobile tire was 50 kg. Further, the room temperature was set to 20 ° C., and the specimen was rotated by driving the turntable so that the tread surface of the automobile tire rolled on the surface of the coating film of the specimen while drawing a circular trajectory having a rotational radius of 125 mm. . The specimen was rotated 300 times at a speed of 60 times / minute. The turning radius indicates a value at the outermost part of the tread surface of the tire.

  The amount of wear loss of the specimen was calculated from the weight of the specimen before the test (9189 g) and the weight of the specimen at the time of 300 revolutions. The weight of the specimen at the time of 300 rotations was 9180 g, and the weight reduction amount was 9 g.

(Slip resistance measurement)
About the asphalt pavement which has a coating film, the slip resistance value of the coating film was measured.

  The sliding resistance value was measured using a pendulum skid resistance tester as follows. The pendulum skid resistance tester measures the resistance value when the edge of a rubber slider attached to the tip of the pendulum slides on the surface of the specimen. The measured value is expressed in BPN (British Pendulum Number), and the larger the value, the less slippery. The measurement was performed several times, and the value when the value was stabilized was adopted as the test value. The BPN value was 72.

(Measurement of water permeability)
About the asphalt pavement which has a coating film, the water permeability of the coating film was measured. The water permeability was measured as follows.

  A 50 mm diameter cylinder part with an open upper end and a bottom part with a diameter of 150 mm and a height of 25 mm is recessed in a substantially conical shape. A test apparatus provided with a bottom plate portion provided with a communicating water flow lower chamber was prepared. The narrowest part of the water channel provided with a cock was 7 mm in diameter.

  First, oily clay was adhered to the entire end surface of the bottom plate portion of the test apparatus, and then the end surface of the bottom plate portion was pressure-bonded to the coating film of the specimen. As a result, when water flows into the water flow lower chamber of the test apparatus, the water can be drained only through the coating film.

  Next, after water was put into the cylinder part, the cock was fully opened to let water flow down, and the time for 400 ml of water to flow down was measured. The flow-down test was performed three times, and the average value of the flow-down time was determined. From this average value, the amount of flowing water per 15 seconds was calculated and used as the water permeability. The water permeability was 1222 ml / 15 s.

[Example 2] (Construction of curable resin composition-2 on asphalt pavement)
(Preparation of the first raw material-2)
For 100 g of the vinyl ester resin VE-1 obtained in Synthesis Example 1, 1.0 g of 125F paraffin wax (manufactured by Nippon Seiwa), 14 g of JR-1000 (made by Teika Co., Ltd., rutile titanium oxide), blue color AA-200 Blue (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 6.0 g as a pigment, AR-300 brown (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 0.4 g as a brown pigment, AY-150 yellow (Kawamura as a yellow pigment) 0.4 g of infrared reflective pigment manufactured by Chemical Co., Ltd., and AG-235 black (infrared reflective pigment manufactured by Kawamura Chemical Co., Ltd.) 6.0 g as a black pigment, N, N-di (β-hydroxyethyl) -p-toluidine (Morin) Chemical Industry Co., Ltd. PT-2HE) 1.5g and 8% cobalt octylate 2.0g were added, and the 1st raw material-2 was prepared.

(Preparation of second raw material-2)
To 100 g of the vinyl ester resin VE-1 obtained in Synthesis Example 1, 1.0 g of 125F paraffin wax (manufactured by Nippon Seiwa) and 4.0 g of 40% pure benzoyl peroxide (Nippa NS, manufactured by Nippon Oil & Fats Co., Ltd.) In addition, a second raw material-2 was prepared.

(Spraying of curable resin composition-2)
A spray test was performed in the same manner as in Example 1 using the spray device 10 including the sprayer 11 shown in FIGS.

  The first raw material-2 made 0.7 Pa · s at 50 ° C. and the second raw material-2 made 0.6 Pa · s at 40 ° C. are supplied to the spraying device 10 6.0 l / min at a time. The curable resin composition-2, which is a mixture of -2 and the second raw material-2, was sprayed from the nozzle part 18 onto the asphalt pavement surface that was the object. Spraying could be done well.

Before the curable resin composition-2 on the surface of the asphalt pavement is cured, 1.0 kg of an anti-slip aggregate with an average particle size of 1.0 mm (trade name Neo Emery, manufactured by Okazaki Huttenus Albertus Kasei Co., Ltd.) / M ^{2 was} sprayed, and curable resin composition-2 was further sprayed thereon. The curable resin composition-2 was sprayed so that the anti-slip aggregate was not exposed.

  When spraying at room temperature after spraying, a coating film having a uniform composition and a thickness of 1.5 mm was formed on the asphalt pavement surface. The content of the anti-slip aggregate in the coating film was 56% by weight.

  About the asphalt pavement which has a coating film, it carried out similarly to Example 1, and measured abrasion resistance.

  When the amount of wear loss of the specimen was calculated from the weight of the specimen before the test (9242 g) and the weight of the specimen at the time of 300 revolutions (9232 g), the weight loss was 10 g.

  About the asphalt pavement which has a coating film, the slip resistance value was measured like Example 1. FIG. The BPN value was 74.

  About the asphalt pavement which has a coating film, it carried out similarly to Example 1, and measured the water permeability. The water permeability was 1220 ml / 15s.

[Comparative Example 1] (Construction of curable resin composition-1 on asphalt pavement)
Same as Example 1 except that the first raw material-1 supplied to the spraying device 10 was adjusted to 2.5 Pa · s at 25 ° C. and the second raw material-1 was adjusted to 2.5 Pa · s at 25 ° C. Then, the curable resin composition-1 was sprayed on the asphalt pavement surface.

  Since the first raw material-1 and the second raw material-1 had high viscosity, poor mixing occurred and spraying was difficult. Although normal temperature curing was attempted after spraying, the curable resin composition-1 was not cured.

[Comparative Example 2] (Measurement of wear resistance of asphalt pavement without coating film)
About the asphalt pavement which does not construct a coating film, it carried out similarly to Example 1, and measured abrasion resistance. When the amount of wear loss of the specimen was calculated from the weight of the specimen before the test (9076 g) and the weight of the specimen at the time of 300 revolutions (9064 g), the weight loss was 12 g.

  About the asphalt pavement which does not construct a coating film, it carried out similarly to Example 1, and measured the slip resistance value. The BPN value was 60.

  About the asphalt pavement which does not construct a coating film, it carried out similarly to Example 1, and measured the water permeability. The water permeability was 1224 ml / 15 s.

  From the above results, it was found that when the first raw material and the second raw material were heated to reduce the viscosity, a coating film having a uniform composition was formed.

  From the above results, it was found that when the coating film is formed, the wear resistance is improved and it is difficult to slip. It was also found that the water permeability was almost the same even when the coating film was formed.

  The spraying device, the method for producing a coating film, and the coating film according to the present invention can be used for coating asphalt pavement surfaces such as asphalt pavement roads and concrete surfaces such as parks, factories, and parking lots.

The figure which shows the spraying system containing the spraying apparatus which concerns on this invention. The front view of the sprayer which comprises the spraying apparatus which concerns on this invention. The top view of the sprayer which comprises the spraying apparatus which concerns on this invention. FIG. 3 is a partial cross-sectional view of FIG. 2 partially cut away in the AA direction. The figure which shows the end surface by the side of the mixer part of a seal | sticker part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Spraying system 10 Spraying apparatus 11 Sprayer 12 Main body part 13 1st fuselage member 14 2nd fuselage member 15 3rd fuselage member 15a The downstream end 16 of the 3rd fuselage member 16 Cap 16a Cap tip 17 Mixer Part 18 Nozzle part 19 Grip 21 First supply valve 22 Second supply valve 23 First supply pipe 24 Second supply pipes 25, 26, 54, 57 Joint 27 First bent pipe 28 Second bent pipe 29 First discharge port 30 Second discharge port 32 Seal portion 32a Seal portion first portion 32b Seal portion second portion 38 Mixer portion chamber 39 Static mixer 40 Supply hose assembly 41 First supply hose 42 First Second supply hose 43a, 43b Insulating member 44 Hose temperature controller 44a Hose temperature controller 44b for the first supply hose Second supply hose Hose temperature controller 46 hose heater cord 47 first hose heater 48 second hose heater 49 hose heater cord connector 50 temperature detector 52 solvent supply valve 53, 55, 56 solvent supply pipe 58 solvent bend Pipe 59 Solvent outlet 61 Air compressor 62a, 62b Air hose 63 Transfer pump 64 Raw material container 64a First raw material container 64b Second raw material container 65 Raw material container heater 66 Raw material container temperature controller 67 Raw material supply hose 70 Hydraulic pressure feeder 71 Hydraulic pressure feeder First supply hose 72 on the outlet side of the second hydraulic pressure feeder second supply hose 73 on the outlet side of the hydraulic pressure pump 76 hydraulic motor 76 solvent pump 77 solvent hose 81 valve operation part 82 valve operation drums 83 and 84 shaft part of the valve operation drum

Claims (15)

A sprayer for mixing and spraying the first raw material and the second raw material;
A first supply hose for supplying the first raw material to the sprayer;
A second supply hose for supplying the second raw material to the sprayer;
A first hose heater for heating the first supply hose;
A second hose heater for heating the second supply hose;
A hose temperature controller capable of independently adjusting each of the heating temperatures of the first and second hose heaters;
A spraying device comprising: A temperature detector for detecting the temperature of the first and second supply hoses;
The hose temperature adjuster can independently adjust the heating temperatures of the first and second hose heaters based on the temperatures of the first and second supply hoses, respectively. Item 4. The spray device according to Item 1. The first hose heater is an electrothermal material that covers at least a part of the first supply hose,
2. The spray device according to claim 1, wherein the second hose heater is an electrothermal material covering at least a part of the second supply hose. The sprayer is
A first discharge port for discharging the first raw material supplied from the first supply hose; and a second discharge port for discharging the second raw material supplied from the second supply hose. The main body,
A mixer unit connected to the first outlet and the second outlet of the main body, and provided therein with a static mixer for mixing the first raw material and the second raw material;
A nozzle part provided at the tip of the mixer part;
The spray apparatus according to claim 1, comprising: The spray device according to claim 4, wherein the mixer unit has a length of a static mixer of 20 cm to 35 cm. A method for producing a coating film using the spray device according to any one of claims 1 to 5,
Spraying a curable resin composition obtained by mixing the first raw material and the second raw material onto an object to form an uncured coating film;
A curing step of curing the uncured coating film to form a coating film that is a cured product of the curable resin composition,
The first raw material includes a liquid vinyl ester resin, a tertiary amine and a reducing agent,
The method for producing a coating film, wherein the second raw material contains a liquid vinyl ester resin and an organic peroxide. The liquid vinyl ester resin includes an epoxy resin, a saturated monobasic acid, a polybasic acid and an unsaturated monobasic acid, a liquid vinyl ester (A) obtained by reacting, a polymerizable unsaturated monomer (B), The method for producing a coating film according to claim 6, wherein the coating film is a mixture of The method for producing a coating film according to claim 6, wherein the organic peroxide is benzoyl peroxide. The method for producing a coating film according to claim 7, wherein the polybasic acid is dimer acid. The method for producing a coating film according to claim 7, wherein the polymerizable unsaturated monomer (B) is a (meth) acrylate monomer. The method for producing a coating film according to claim 6, wherein the tertiary amine is an aromatic tertiary amine. The method for producing a coating film according to claim 6, wherein at least one of the first raw material and the second raw material further includes a paint raw material. Sprinkling anti-slip aggregate on the surface of the uncured coating, and forming an aggregate-embedded uncured coating in which at least a part of the anti-slip aggregate is embedded;
Spraying the curable resin composition on the surface of the aggregate-buried uncured coating to form an aggregate-containing uncured coating containing the anti-slip aggregate; and
And a step of curing the aggregate-containing uncured coating film to form a coating film that is a cured product of a curable resin composition including the anti-slip aggregate. A method for producing a coating film. The method for manufacturing a coating film according to claim 6 or 13, wherein the object is an asphalt pavement surface or a concrete surface. A coating film produced by the coating film manufacturing method according to any one of claims 6 to 14.

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