JP4149185B2 - Resin plate for concrete formwork - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention is a resin plate for imparting a concavo-convex pattern on a concrete surface, excellent in dimensional stability, excellent in releasability from hardened concrete, and capable of improving the curability of the concrete surface. The present invention relates to a resin plate for formwork.
[0002]
[Prior art]
In recent years, various methods for producing concrete have been proposed in which a concavo-convex pattern is imparted to the concrete surface to enhance design. For example, a rubber plate is engraved using a blade and a surface is provided with a concavo-convex pattern. A metal or plastic mold with a pattern is prepared, and the mold and the rubber plate are stacked and hot pressed. In Japanese Patent Laid-Open Nos. 1-171807 and 3-63354, a method of producing a resin plate having a concavo-convex pattern using photolithography is shown. .
[0003]
In the conventional method, in the uneven pattern formed on the surface of the rubber plate or the resin plate, there is a thick rubber layer or resin layer of several mm in some cases at the bottom of the concave portion, so that it is formed on the surface of these plates. When the pattern was transferred to the concrete, the thickness of the concrete was reduced by the thickness of the rubber layer or resin layer remaining on the bottom of the concave portion of the plate. For example, in the case of a concrete secondary product whose standard is determined, such as a U-shaped groove lid, it has a problem that it is necessary to modify the dimensions of the concrete formwork to reduce the thickness. It was. Therefore, it was necessary to make the thickness W of the rubber layer or the resin layer remaining at the bottom of the concave portion of the plate shown in FIG. 2 as thin as possible. Left platemaking problems such as the pattern being cut off. Japanese Laid-Open Patent Publication No. 1-171807 describes a method for producing a resin plate having a concavo-convex pattern using a photosensitive resin and photolithography. In this method, a photosensitive resin layer is formed on a sheet-like base material, light is first applied to the entire surface of the photosensitive resin layer from the sheet-like base material side, a base portion is formed thick, and the other side is further formed. In this method, light passing through a negative film is irradiated from the surface to cure the photosensitive resin, and a concavo-convex pattern is formed through a development process. Therefore, there is a thick resin layer at the bottom of the recess, which does not solve the problem of the resin remaining at the bottom of the recess, which has been a problem with conventional rubber plates.
[0004]
In any of these methods, a rubber plate or a resin plate having a concavo-convex pattern is fixed to a concrete mold made of metal such as iron or aluminum, natural wood or plywood, or plastic using an adhesive, etc. Before pouring into the mold, by applying a release agent mainly composed of mineral oil, heavy oil, paraffin, grease, petroleum jelly, soapy water, etc. to the surface of the rubber plate or resin plate, It is easy to remove from the formwork. In addition, the release agent is applied each time before pouring concrete because the release effect is not sustainable. Furthermore, since a generally used release agent inhibits the curing reaction of the concrete surface, the curing of the surface is slow, and it takes a long period of time for complete curing, typically about one month. In the meantime, it was necessary to store the produced concrete product as it was, which left a big problem that the productivity was extremely low.
[0005]
In addition, when curing concrete, it includes a step of maintaining at a high temperature of 60 to 80 ° C. for several hours, and furthermore, because it comes into contact with a strong alkaline raw cocrete, conventional rubber plates and resin plates are also in terms of dimensional stability. I left a problem.
Moreover, since bubbles and bubble marks are generated on the formed concrete surface, it is difficult to faithfully transfer the uneven pattern on the surface of the resin plate. Further, since the surface is contaminated with stains due to the release agent, when the appearance is impaired due to discoloration and the appearance is required, there is a problem that a process for repairing the entire surface is required.
Furthermore, the uneven pattern formed on the concrete surface from the viewpoint of design properties is a mixture of patterns of extremely various dimensions. Therefore, a resin plate that can be formed as designed up to a pattern with a fine dimension is desired. From this viewpoint, a photosensitive resin material that can form a cured product with high resolution and high durability is required. It was.
[0006]
[Problems to be solved by the invention]
Resin plate for concrete formwork with high dimensional accuracy, excellent releasability, and capable of forming a concavo-convex pattern that faithfully copies the pattern of the resin plate on the concrete surface, and excellent durability that can be used repeatedly Provide a method.
[0007]
[Means for Solving the Problems]
  As a result of intensive studies, the present inventorsSizeBy using a plate with a convex pattern on the surface of a rubber layer or resin layer formed on the surface of a thin sheet-like substrate with high method stability and engraving with a laser, the resin plate is applied to the surface of the hardened concrete. A concave pattern corresponding to the convex pattern on the surface can be faithfully transferred, and a decrease in the thickness of the concrete can be suppressed to a low level by using a thin sheet-like substrate. Furthermore, the concrete hardened by heat curing can be easily taken out from the formwork, and it has been found that a surprising effect that cannot be considered with a conventional resin plate is exhibited, and the present invention has been completed. That is, this invention provides the following as a resin plate for concrete formwork in order to solve the said subject. The resin plate of the present invention is used by sticking to the surface of metal, wooden or plastic formwork, and is used in the factory for road concrete products, concrete products for river maintenance, concrete products for slopes, concrete products for building land, etc. It is used for concrete secondary products manufactured by, or concrete structures constructed by the on-site concrete method.
[0008]
  The first of the present invention is a resin plate comprising a sheet-like substrate and a photosensitive resin cured product layer having a convex pattern formed by laser engraving, which is used by being mounted on the surface of a concrete mold, The substrate is 0.01 mm to 1 mm in thickness, and the photosensitive resin composition comprises (A) a plurality of polycarbonate diol segments bonded via a urethane bond, and has an ethylenically unsaturated group at at least one end. A cured product of a photosensitive resin composition comprising a polyurethane prepolymer, (B) a reactive monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator, the cured photosensitive resin The convex pattern has a height of 0.01 mm or more and 50 mm or less, and the thickness of the resin residual layer where the convex pattern does not exist is 10% or less of the convex pattern. There in the concrete formwork for the resin plate is;
[0009]
  First of the present inventiontwoIsA concrete form obtained by mounting the resin plate according to the preceding paragraph 1 on the surface of the concrete form through an adhesive layer;
[0010]
  First of the present inventionthreeIs(A) on the surface of a sheet-like substrate having a thickness of 0.01 mm or more and 1 mm or less.An unsaturated polyurethane prepolymer comprising a plurality of polycarbonate diol segments bonded via a urethane bond and having an ethylenically unsaturated group at at least one terminal; (B) a reactive monomer having at least one ethylenically unsaturated bond And (C) a photopolymerization initiatorA liquid photosensitive resin composition layer is provided, and the entire surface of the liquid photosensitive resin layer is irradiated with high energy rays to cure the photosensitive resin layer, and further, the cured photosensitive resin layer is removed by irradiation with a laser. By forming a convex pattern of a cured photosensitive resin having a height of 0.01 mm or more and 50 mm or less on the sheet-like base material, the thickness of the resin remaining layer without the convex pattern is set to a convex pattern. Less than 10%It is characterized byRucoThis is a method for producing a resin plate for a mold formwork.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described.
The linear thermal expansion coefficient of the sheet-like substrate used in the present invention is 100 ppm / ° C. or less, preferably 80 ppm / ° C. or less, more preferably 70 ppm / ° C. or less. When the coefficient of linear thermal expansion exceeds 100 ppm / ° C, the resin plate attached to the surface of the concrete mold warps or peels off during the curing process at high temperatures of the concrete, and the pattern on the surface of the resin plate is faithfully transferred. It becomes difficult. In the present invention, the linear thermal expansion coefficient is measured using a thermomechanical measurement method.
[0012]
The melting temperature of the sheet-like substrate used in the present invention is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 220 ° C. or higher. The melting temperature is a temperature at which the resin is fluidized. In the present invention, the melting temperature is measured using a differential scanning calorimetry, and is defined as a peak temperature that appears on the endothermic reaction side when the temperature is gradually raised from room temperature. The higher this temperature, the higher the dimensional stability. When the melting temperature is less than 150 ° C., the sheet-like substrate is likely to be deformed in a temperature environment of 60 ° C. to 80 ° C. used for curing the concrete.
[0013]
The thickness of the sheet-like substrate used in the present invention is from 0.01 mm to 1 mm, preferably from 0.03 mm to 0.05 mm, and more preferably from 0.05 mm to 0.02 mm. When the thickness is less than 0.01 mm, there is a problem of wrinkling or cutting when handling the sheet-like base material, and when the thickness exceeds 1 mm, there is a problem that the thickness dimension of the hardened concrete becomes thin.
As the material of the sheet-like substrate used in the present invention, polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, Examples thereof include polyethersulfone resins, liquid crystal resins made of wholly aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins. Further, these resins can be laminated and used. For example, a sheet in which a layer of polyethylene terephthalate having a thickness of 50 μm is laminated on both surfaces of a wholly aromatic polyamide film having a thickness of 4.5 μm.
[0014]
Examples of a method for reducing the linear thermal expansion coefficient of the sheet-like substrate include a method of adding a filler, a method of impregnating or coating a resin on a mesh cloth such as wholly aromatic polyamide, a glass cloth, or the like. it can. As the filler, generally used organic fine particles, inorganic fine particles such as metal oxide or metal, organic / inorganic composite fine particles, and the like can be used. In addition, porous fine particles, fine particles having cavities inside, microcapsule particles, and layered compound particles in which a low molecular compound intercalates can be used.
In particular, metal oxide fine particles such as alumina, silica, titanium oxide, and zeolite, latex fine particles made of polystyrene / polybutadiene copolymer, and natural organic fine particles such as cellulose are useful.
[0015]
By performing physical and chemical treatments on the surface of the sheet-like substrate used in the present invention, the adhesiveness with the photosensitive resin composition layer or the adhesive layer can be improved. Examples of the physical treatment method include a sand blast method, a wet blast method for injecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation method, and the like. The chemical treatment method includes a strong acid / strong alkali treatment method, an oxidant treatment method, a coupling agent treatment method, and the like.
[0016]
  The method of forming a resin convex pattern on the surface of a sheet-like substrate is as follows:, LesExamples of the method include removing the resin by melting or ablation by irradiating a laser. In the convex pattern formed on the surface of the sheet-like substrate, the height of the convex portion is 0.01 mm or more and 50 mm or less, preferably 0.1 mm or more and 50 mm or less, and more preferably 0.5 mm or more and 30 mm or less. If the height is less than 0.01 mm, it is insufficient for imparting design properties to the concrete surface, and if it exceeds 50 mm, it becomes difficult to remove the hardened concrete from the formwork.
[0017]
  Moreover, it is preferable that the thickness of the resin layer remaining on the surface of the portion where the convex pattern does not exist on the surface of the sheet-like substrate on which the convex pattern is formed is as thin as possible. The thickness of the resin residual layer is 10% or less, preferably 5% or less, more preferably 1% or less of the height of the convex pattern. If the thickness of the residual resin layer is greater than 10% of the height of the convex pattern, the thickness of the hardened concrete will be thin, and the depth of the concave pattern transferred to the concrete will be shallow, so Will fall outside the standard. LesIn the method of irradiating the laser beam and removing the resin layer, the amount of digging can be easily adjusted to 10% or less of the height of the convex pattern by controlling the intensity of the laser beam and the irradiation time. This method has the feature that the size of the pattern that can be processed can be made about the beam diameter of the laser beam because the beam diameter of the laser beam can be reduced to 50 μm or less.
[0018]
  Furthermore, the convex pattern formed on the surface of the sheet-like substrate in the present invention has a taper in the direction of the sheet-like substrate. That is, as shown in FIG. 3, the taper angle R from the top direction of the convex pattern to the sheet-like substrate direction is preferably 50 ° or more and 85 °.
The taper angle is preferably 50 ° or more from the viewpoint of forming a pattern with a predetermined height at a high density, and preferably 85 ° or less from the viewpoint of mold release of the hardened concrete..
[0019]
In the method of irradiating a laser beam to ablate and melt and remove the resin, a concavo-convex pattern can be formed directly without going through a development step. Typical lasers that can be used include those having an oscillation wavelength in the infrared region such as carbon dioxide laser and YAG laser, and those having an oscillation wavelength in the ultraviolet region such as the third and fourth harmonics of the YAG laser and excimer laser. Laser.
Next, the photosensitive resin composition capable of forming a cured product having high resolution and high durability, which can be used for the resin form for concrete molds of the present invention, will be described.
[0020]
  FeelingThe component (A) constituting the light-sensitive resin composition is preferably a prepolymer having a number average molecular weight of 1,000 to 500,000. Examples of condensation polymers include polyurethane resins, polyester resins, unsaturated polyester resins, polyimide resins, polysulfone resins, polyamide resins, and polycarbonate resins. Examples of addition polymerization polymers include polyolefins such as polystyrene resins, polyethylene resins, and polypropylene resins. Polybutadiene resins such as homopolymers or copolymers, and ring-opening polymerization polymers include epoxy resins and polysiloxanes. In the case of a prepolymer having a number average molecular weight of less than 1000, it is difficult to ensure the mechanical properties and flexibility of a cured product formed by irradiating high energy rays. When the number average molecular weight exceeds 500,000, the viscosity of the photosensitive resin composition Greatly increases, and when the uncured product is removed in the development step, it becomes difficult to dissolve or disperse in the developer. Preferably it is 2000 or more and 100,000 or less, More preferably, it is 2000 or more and 25000 or less. The number average molecular weight of the present invention is measured by a gel permeation chromatography (GPC) method, and is determined by conversion with polystyrene having a very narrow molecular weight distribution and a known molecular weight.
[0021]
In the photosensitive resin composition used in the present invention, an unsaturated polyurethane prepolymer is particularly preferable as the prepolymer component (A). First, a diol compound and a diisocyanate compound are reacted to obtain a polyurethane, and then this polyurethane is reacted with a hydroxyl group or amino group-containing ethylenically unsaturated compound or an isocyanate group-containing ethylenically unsaturated compound.
[0022]
Examples of the diol compound for obtaining the polyurethane include compounds having two hydroxyl groups in one molecule, such as polypropylene glycol adipate diol, polyneopentyl glycol adipate diol, polybutylene glycol adipate diol, polycaprolactone diol, and polyvalerolactone diol. Examples include polyester diols, polyether diols such as polyethylene glycol diol, polypropylene glycol, and polytetramethylene glycol, and polycarbonate diols.
[0023]
The molecular weight determined from the hydroxyl value of the diol compound is usually about 400 to 5000, but from the viewpoint of obtaining a more flexible and strong polyurethane, it is preferable to use a molecular weight of about 500 to 2500.
Examples of the diisocyanate compound for obtaining the polyurethane include compounds having two or more isocyanate groups, such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate. Of these, tolylene diisocyanate is preferred in that it does not increase the viscosity of the resulting polyurethane so much and is easy to obtain a flexible and strong one.
[0024]
Examples of the hydroxyl group-containing ethylenically unsaturated compound to be reacted with the polyurethane include hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, N-methylol acrylamide, polyoxyethylene glycol monomethacrylate, polyoxypropylene glycol monomethacrylate, etc. As an example. Of these, hydroxyethyl methacrylate and hydroxypropyl methacrylate are preferable from the viewpoint of flexibility and strength, and hydroxypropyl methacrylate having excellent water resistance is most preferable.
[0025]
Examples of the isocyanate group-containing ethylenically unsaturated compound to be reacted with the polyurethane include compounds obtained by adding a hydroxyl group-containing ethylenically unsaturated compound and a diisocyanate compound in a ratio of 1: 1.
[0026]
When a hydroxyl group-containing ethylenically unsaturated compound is used for the preparation of the unsaturated polyurethane, first, a terminal-end isocyanate group polyurethane is synthesized by a reaction of the diol compound and the diisocyanate compound, and this is reacted with a hydroxyl group-containing ethylenically unsaturated compound. In this case, in order to suppress the side reaction and complete the reaction in a short time, the hydroxyl group-containing ethylenically unsaturated compound is usually added in an excess of about 2 to 5 times the equivalent amount with respect to the both-end isocyanate group polyurethane. It is preferable to obtain a mixture of a saturated bond-containing polyurethane and an excess of a hydroxyl group-containing ethylenically unsaturated compound.
[0027]
On the other hand, when using an isocyanate group-containing ethylenically unsaturated compound for the preparation of unsaturated polyurethane, first, a hydroxyl group polyurethane at both ends is synthesized by reacting the diol compound and the diisocyanate compound, and this is reacted with an isocyanate group-containing ethylenically unsaturated compound. Let In this case, the isocyanate group-containing ethylenically unsaturated compound is generally added in such a range that the number of isocyanate groups is the same as or less than the number of hydroxyl groups of both-end hydroxyl group polyurethane. In order to suppress side reactions, it is preferable to reduce the viscosity of the reaction system by adding a component that does not participate in the urethanization reaction as a diluent. When an isocyanate group-containing ethylenically unsaturated compound is excessively added to the both-end hydroxyl group polyurethane, it is preferable to eliminate the excess isocyanate group by adding a compound having an active hydrogen such as a hydroxyl group after completion of the reaction.
[0028]
Furthermore, polar groups such as carboxyl groups can be introduced into the unsaturated polyurethane. The introduction of the carboxyl group into the unsaturated polyurethane is, for example, by adding an ethylenically unsaturated compound containing two hydroxyl groups to the both-end isocyanate group polyurethane and reacting one of the hydroxyl groups with an isocyanate group to produce two hydroxyl groups. And an unsaturated polyurethane having two ethylenically unsaturated bonds, and by further adding an acid anhydride to cause a ring-opening reaction with the hydroxyl group of the polyurethane, both ends have a carboxyl group and an ethylenically unsaturated bond. It can be an unsaturated polyurethane.
[0029]
As the ethylenically unsaturated compound containing two hydroxyl groups used here, a compound obtained by adding water to glycidyl methacrylate or acrylate to open an epoxy group, and having a hydroxyl group bonded to primary carbon and secondary carbon Is used. By utilizing the difference in reactivity between the primary carbon-bonded hydroxyl group and the secondary carbon-bonded hydroxyl group, an unsaturated polyurethane having hydroxyl groups at both ends in which only one hydroxyl group in the molecule has reacted with the isocyanate group can be obtained.
[0030]
Examples of the acid anhydride used for introducing a carboxyl group by ring-opening reaction with a hydroxyl group include succinic acid, phthalic anhydride, and maleic anhydride. In place of the unsaturated polyurethane, an unsaturated polyester can be used as an additive component. The unsaturated polyester is obtained by a dehydration condensation reaction between a diol compound and an ethylenically unsaturated bond-containing dicarboxylic acid compound. Alternatively, both terminal hydroxyl groups or both terminal carboxyl group polyesters are synthesized by dehydration condensation reaction from a diol compound and a dicarboxylic acid compound, and then an ethylenically unsaturated compound having a functional group capable of reacting with these terminal functional groups is reacted. Can also be obtained.
[0031]
Examples of the diol compound include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and butanediol.
Dicarboxylic acid compounds include adipic acid, azelaic acid, sebacic acid, isophthalic acid, succinic acid, phthalic anhydride, terephthalic acid and other ethylenically unsaturated dicarboxylic acids such as fumaric acid, maleic acid and maleic anhydride. It can be illustrated.
[0032]
  HeavyReactive monomer having a compatible reactive group(B)As a monomer having an ethylenically unsaturated group such as a vinyl group, an acrylic group or a methacrylic group, or a cyclic ether such as epoxy or oxetane, or a ring-opening polymerizable reactive group such as cyclic carbonate, lactone, lactam or cyclic acetal. Mention may be made of monomers. The number of polymerizable reactive groups in the monomer may include one monofunctional monomer, but it is preferable that the polyfunctional monomer having 2 or more is 10 wt% or more, preferably 20 wt% or more of the total monomer weight. However, when the polyfunctional monomer having 3 or more polymerizable reactive groups is contained in an amount of 50 wt% or more of the total monomer weight, the viscosity of the photosensitive resin composition is significantly increased, and the subsequent processability is deteriorated. A compound having an ethylenically unsaturated group and a ring-opening polymerizable reactive group simultaneously in the molecule may also be used. Furthermore, a monomer having an ethylenically unsaturated group and a monomer having a ring-opening polymerizable reactive group can be mixed and used.
[0033]
Specific examples of the monomer having an ethylenically unsaturated group used in the present invention include acrylamide (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, Isobornyl (meth) acrylate, diacetone acrylamide, isobutoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate , Dicyclopentanediene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, lauryl (meth) acrylate polyethylene glycol mono (meth) acrylate, poly Monofunctional monomers such as propylene glycol mono (meth) acrylate, methyltriethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate Bifunctional monomers such as pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tri (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylol Raise polyfunctional monomers such as propane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate be able to.
[0034]
In addition, as a monomer having a ring-opening polymerizable reactive group, an epoxy compound, an oxetane compound, a cyclic ester compound, a dioxolane compound, a spiro ortho carbonate compound, a spiro ortho ester compound, a bicyclo ortho ester compound, a cyclosiloxane compound, a cyclic imino ether compound, Examples thereof include a cyclic imine compound, a bicyclic urea compound, a cyclic carbonate compound, a cyclic sulfite compound, and a lactam compound. The ring-opening polymerizable compound of the present invention has one or more, preferably two or more ring-opening polymerizable reactive groups in the molecule.
[0035]
Among the ring-opening polymerization reactive monomers, the epoxy compound which is a particularly highly reactive compound is preferably a compound having two or more groups having an epoxy bond such as a glycidyl group or an epoxycyclohexyl group in the molecule. As specific examples, compounds obtained by reacting epichlorohydrin with polyols such as various diols and triols, that is, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl Ether, trimethylolpropane triglycidyl ether Bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl ether of a compound obtained by adding ethylene oxide or propylene oxide to bisphenol A, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether , Poly (ethylene glycol adipate) diol diglycidyl ether, poly (caprolactone) diol diglycidyl ether, and the like. As another example, a polyepoxy compound obtained by reacting a compound having two or more olefins in the molecule with peracid such as peracetic acid, that is, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexyl. Carboxylate, 1-methyl-3, 4-epoxycyclohexylmethyl-1′-methyl-3 ′, 4′-epoxycyclohexyl carboxylate, bis [1-methyl-3,4-epoxycyclohexyl] ester adipate, vinylcyclohexene Examples thereof include polyepoxy compounds obtained by reacting peracetic acid with polydienes such as diepoxide, polybutadiene and polyisoprene, and epoxidized soybean oil.
[0036]
Moreover, as an oxetane compound used by this invention, the compound used normally can be used, Although it does not specifically limit, Xylylene oxetane (the Toagosei Co., Ltd. brand name "OXT-121") , 3-ethyl-3-hydroxymethyloxetane (trade name “OXT-101” manufactured by Toa Gosei Co., Ltd.), trade names “OXT-221”, “PNOX-1009” produced by Toa Gosei Co., Ltd. and the like. Examples of the cyclic ester compound include compounds having an ε-caprolactone ring, a γ-butyrolactone ring, and a β-propionlactone ring. Further, it may be a compound having different ring-opening polymerizable reactive groups in one molecule.
[0037]
  lightPolymerization initiator(C)Examples thereof include a photo radical generator and a photo acid generator. As the photoradical generator, those usually used can be used. Specific examples include 4-phenoxydichloroacetophenone, 2-t-butyltrichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2. -Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenyl (4-dodecyl) propan-1-one, 4- (2-hydroxydiphenyl) -2-hydroxy-2-methyl Propan-1-one, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether, benzy Dimethyl ketal, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, chlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3'-dimethyl-4-methoxybenzophenone 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-isopropylthioxanthone, α-acyloxime ester, Acylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrenequinone, camphorquinone, benzyl, 3,3 ′, 4,4′-tetra (t-butyl Tilperoxycarbonyl) benzophenone, dibenzosuberone, 2-ethylanthraquinone, triethanolamine, methyldiethanolamine, triisopropanolamine, Michler's ketone, 4,4′-diethylaminophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Acid (n-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid and the like.
[0038]
As a specific example of the photoacid generator, BF is used as a counter ion._Four-PF₆-SbF₆A triarylsulfonium salt, a diaryliodonium salt, an aryldiazonium salt, and the like, and a commercially available photocationic polymerization initiator such as triarylsulfonium hexafluorophosphate, p-thiophenoxyphenylsulfonium hexafluorophosphate may be used. it can. These function to generate an acid such as Lewis acid or Bronsted acid by irradiation with high energy rays to cause a curing reaction. From the viewpoint of curability, triarylsulfonium salts are preferred. Of these, triarylsulfonium hexafluorophosphate is excellent in terms of thick film curability.
[0039]
As for the photoinitiator used by this invention, 0.1-10 wt% is preferable with respect to the total weight of a prepolymer component (A) and a reactive monomer component (B). If it is less than 0.1 wt%, the concentration of radical species or acid generated by absorbing actinic radiation tends to be low, and the curing reaction does not proceed sufficiently. On the other hand, when the amount exceeds 10 wt%, a reaction product that absorbs high energy rays and generates radical species or acid tends to remain in a large amount in the cured product, which tends to lower the mechanical properties of the cured product.
[0040]
In the present invention, the resin plate may contain a filler having a number average particle size of 0.1 μm or more and 100 μm or less. More preferred are fine particles having a number average particle size of 0.1 μm or more and 10 μm or less. When the number average particle diameter is less than 0.1 μm, the viscosity of the photosensitive resin composition is increased and the defoaming tends to be difficult. On the other hand, if it exceeds 100 μm, it tends to be difficult to form a fine pattern.
[0041]
Specific examples of fillers include metal oxides such as titanium oxide, calcium carbonate, magnesium carbonate, silica, and alumina, talc, chromate, ferrocyanide, various metal sulfates, sulfides, selenides, and phosphoric acid. Inorganic pigments such as salts, organic pigments such as phthalocyanine, quinacridone, isoindolinone, perinone, and dioxazine, carbon black, gold, silver, copper, platinum, palladium, nickel, aluminum, silicon, brass, etc. The metal simple substance or alloy fine particle of this, the metal powder which coat | covered the surface with a different metal, the coloring filler which disperse | distributed the pigment or dye in the fine particle formed from an organic compound, etc. can be mentioned.
[0042]
Further, as the filler to be contained in the photosensitive resin composition in the present invention, a filler having a hydroxyl group on the surface is particularly preferable. The filler having a hydroxyl group on the surface has high adhesiveness to the resin composition, and particularly those exposed on the surface of the resin plate can react with the coupling agent to modify the surface of the resin plate. Is possible. Examples of the filler having a hydroxyl group on the surface include metal oxides such as alumina, silica, titanium oxide, and zeolite, and natural organic fine particles such as cellulose.
[0043]
When the particle size distribution of the powder or particles used as the filler in the present invention is wide, the filling rate becomes high when the colorant is contained at a high concentration, so that the actinic ray permeability decreases. The shape of the colorant used in the present invention is not particularly limited, and any shape such as a spherical shape, a flat shape, or a polyhedral shape may be used.
The content of the filler used in the present invention is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less with respect to 100 parts by weight of the resin composition. is there.
In addition, by including the organic fine particles, particularly fluorine fine particles such as tetrafluoroethylene, the releasability from the hardened concrete can be improved. Further, by including ceramic fine particles such as boron nitride, silicon nitride and silicon carbide, the wear resistance of the resin plate can be improved.
[0044]
In the resin plate for concrete mold of the present invention, the thickness between the sheet-like substrate and the photosensitive resin composition layer is 0.001 μm to 100 μm, preferably 0.05 μm to 20 μm, more preferably 0.05 μm. The adhesive layer having a thickness of 10 μm or less can be inserted, and has an effect of improving the adhesion between the sheet-like substrate and the photosensitive resin composition layer. From the viewpoint of securing sufficient adhesive strength, the thickness of the adhesive layer is preferably 0.001 μm or more and 100 μm or less from the viewpoint of suppressing the occurrence of warpage due to heat. The adhesive used for forming the adhesive layer is not particularly limited, and those usually available such as a thermosetting adhesive and a photocurable adhesive can be used.
[0045]
In the resin plate for concrete mold of the present invention, the surface on the side where the convex pattern is formed can be modified using a coupling agent. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, a chromium coupling agent, and an aluminum coupling agent.
A widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the surface hydroxyl group of the substrate. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group. Group, trichlorosilyl group, diethoxysilyl group, dimethoxysilyl group, dimonochlorosilyl group, monoethoxysilyl group, monomethoxysilyl group, monochlorosilyl group. Further, at least one of these functional groups exists in the molecule, and is immobilized on the surface of the base material by reacting with the surface hydroxyl group of the base material. Further, the compound constituting the silane coupling agent of the present invention is selected from acryloyl group, methacryloyl group, active hydrogen-containing amino group, epoxy group, vinyl group, perfluoroalkyl group, and mercapto group as reactive functional groups in the molecule. Those having at least one functional group or those having a long-chain alkyl group can be used. The structure is not particularly limited,
[0046]
To give specific examples, the following groups (a) to (g) can be selected and used.
(A) having an acryloyl group
γ-acryloxypropyltrimethoxysilane
(B) having a methacryloyl group
γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane
(C) having an active hydrogen-containing amino group
γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-ureidopropyl Triethoxysilane and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane
[0047]
(D) having an epoxy group
γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
(E) having a vinyl group
Vinyltriethoxysilane and vinyltrimethoxysilane
(F) having a mercapto group
γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane
[0048]
(G) having a perfluoroalkyl group
CF_ThreeCH₂CH₂Si (OCH_Three)_Three, CF_Three(CF₂)_FiveCH₂CH₂Si (OCH_Three)_Three,
CF_Three(CF₂)_FiveCH₂CH₂Si (OCH_Three)_Three, CF_Three(CF₂)₇CH₂CH₂Si (OCH_Three)_Three,
CF_Three(CF₂)_FiveCH₂CH₂SiCH_Three(OCH_Three)₂, CF_Three(CF₂)₇CH₂CH₂SiCH_Three(OCH_Three)₂,
CF_ThreeCH₂CH₂SiCl_Three, CF_Three(CF₂)_FiveCH₂CH₂SiCl_Three, CF_Three(CF₂)₇CH₂CH₂SiCl_Three
[0049]
Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (octylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyl Dimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate Over DOO, isopropyl tri (dioctyl sulfate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) may include compounds such as titanates.
The above coupling agent is adjusted by diluting with a water-alcohol or acetic acid water-alcohol mixture as necessary. The concentration of the coupling agent in the treatment liquid is preferably 0.05 to 10.0% by weight.
[0050]
The coupling agent treatment method will be described. The treatment liquid containing the coupling agent is applied to a resin plate for concrete formwork. The method for applying the coupling agent treatment liquid is not particularly limited, and for example, an immersion method, a spray method, a roll coating method, or a brush coating method can be applied. Further, the coating treatment temperature and the coating treatment time are not particularly limited, but are preferably 5 to 60 ° C., and the treatment time is preferably 0.1 to 60 seconds. Furthermore, it is preferable to dry the treatment liquid layer on the surface of the resin plate under heating, and the heating temperature is preferably 50 to 150 ° C.
[0051]
The produced resin plate for concrete formwork is used by being attached to the concrete formwork surface through an adhesive layer. As the adhesive, those which are usually available such as a double-sided adhesive sheet and a spray adhesive can be used. In particular, when a resin plate is used after being replaced, it is necessary to remove it easily. Therefore, an adhesive sheet of a type that is foamed by heating and whose adhesive strength becomes extremely small, such as a trademark “River” manufactured by Nitto Denko Corporation. It is also effective to use “alpha”.
[0052]
Generally, nondestructive inspection such as a Schmidt hammer test is widely performed as a method for evaluating the cured material properties of hardened concrete. This method is a method of hitting a steel ball on the concrete surface, and is known as a method of estimating the strength without destroying the concrete. According to this method, concrete with high strength is a method for estimating the strength of concrete indirectly by utilizing the characteristic that the degree of repulsion of steel balls is large and the strength of concrete with low strength is small. In the present invention, as a method that can be more simply evaluated based on this method, a steel ball having a diameter of 10.9 mm and a weight of 5.4 g is dropped from a height of 30 cm onto a concrete surface, and the steel ball is repelled. A method for measuring the thickness was used.
[0053]
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
[0054]
[referenceExample 1]
  [Prepolymer production]
  80 parts by weight of a polyoxyethylene (EO) -polyoxypropylene (PO) block copolymer diol having a number average molecular weight of 2500 (EO / PO molar ratio 1/4) and 0.1 parts by weight of dibutyltin dilaurate as a catalyst; 0.8 part by weight of 6-t-butyl-4-methylphenol was placed in a reaction vessel and mixed with stirring. Into this, 8.9 parts by weight of tolylene diisocyanate was added dropwise with stirring at an external temperature of 40 ° C., and then the external temperature was gradually raised and reacted at 80 ° C. for about 5 hours. Furthermore, 11.5 parts by weight of 2-hydroxypropyl methacrylate was added and mixed well for about 2 hours. As a result, an unsaturated polyurethane prepolymer a was obtained.
[0055]
[Adjustment of photosensitive resin composition]
16 parts by weight of ethylene glycol dimethacrylate, 0.4 parts by weight of photopolymerization initiator 2,2-dimethoxy-2-phenylacetophenone, and polymerization inhibitor 2,6-t-butyl-based on 80 parts by weight of unsaturated polyurethane prepolymer a 4-methylphenol 0.05 weight part was mixed and the photosensitive resin composition A was obtained.
[0056]
[Preparation of resin plate]
Asahi Kasei Co., Ltd., flexographic plate making machine, trademark “AWF plate making machine” glass surface is coated with an adhesive with a thickness of several μm on one side of a transparent polyethylene terephthalate film with a thickness of 180 μm The film was placed so that the surface on which the adhesive layer was applied was on top, and vacuum-adhered. On the base film, the photosensitive resin composition A was molded and spread to a thickness of 2.5 mm using a carriage manufactured by Asahi Kasei Corporation and a negative film for forming a convex pattern. FIG. 1A shows this state. The carriage is a traveling molding and spreading device having a laminate roller, a bucket (resin reservoir), a negative film, a guide, and the like. A spacer along the glass surface (a rail that moves up and down to regulate the thickness of the plate) ) A device that casts the photosensitive resin composition to a predetermined thickness while casting the photosensitive resin composition while running on top and feeding a negative film. The negative film has a heat-sensitive material coated on one side of a transparent polyester film having a thickness of 120 μm, and has been designated by the user in advance using CAD data using a thermal head printer (trade name “thermal plotter” manufactured by Ricoh). It is a negative film of a resin plate for concrete formwork produced by outputting an image in which symbols and characters are input. Since the heat-sensitive material in contact with the thermal head changes to black, in the negative film, the blackened portion does not transmit high energy rays. The minimum dimension of this black light shielding part was 3 mm.
[0057]
Next, the photosensitive resin composition A was cured by irradiating ultraviolet rays from the upper part of the obtained laminate with an exposure device provided in the plate making machine. 1 (b) and 1 (c) show this state (FIG. 1 (b) downward → schematically shows ultraviolet irradiation). After the exposure is completed, the negative film is peeled off, and the uncured portion that has not been irradiated with ultraviolet rays is scraped off with a spatula, and then the uncured portion is removed with a weak alkaline detergent (trade name “W-10” manufactured by Asahi Kasei Co., Ltd.). Completely removed. Furthermore, ultraviolet rays were irradiated in water to completely cure the resin plate, and then water was removed using a hot air dryer to obtain a resin plate for concrete formwork. That is, a resin plate (A) having a height of 2.5 mm and having substantially only a convex pattern was obtained on a sheet-like substrate having a thickness of 180 μm. The thickness of the resin plate was uniform, and the accuracy was within ± 10 μm. FIG. 1 (d) shows this state.
[0058]
The taper angle of the convex pattern formed on the surface of the sheet-like substrate was 83 °.
Further, the thickness of the resin remaining layer remaining on the portion other than the convex pattern on the surface of the sheet-like substrate was 10 μm or less, and this value was 0.4% or less of the height of the convex pattern.
The linear thermal expansion coefficient of the polyethylene terephthalate base film, which is the sheet-like substrate, is 50 ppm / ° C. as a result of measurement using a thermomechanical measurement device (trade name “TMA-50” manufactured by Shimadzu Corporation). The melting temperature measured by a differential scanning calorimeter (trade name “DSC-60” manufactured by Shimadzu Corporation) was 245 ° C.
[0059]
[Paste to concrete formwork]
A spray adhesive was applied to the surface of the resin mold (a) for concrete mold obtained as described above on the side where the convex pattern does not exist, and was attached to an iron concrete mold.
[0060]
[Transfer of pattern to concrete surface]
Poured ready-mixed concrete consisting of 100 parts by weight of Pordoland cement, 200 parts by weight of sand, 300 parts by weight of gravel and 60 parts by weight of water in a mold, heated in a steam bath at 70-75 ° C. for 4 hours, and then at room temperature. The concrete was hardened by cooling for 30 minutes. Hardened concrete is easily released from the metal formwork, and the resulting concrete surface is smooth and free of any deposits. The photosensitive resin applied in the formwork is also completely on the formwork surface. It remained attached. On the surface of the hardened concrete, a concave pattern in which the convex pattern of the resin plate was completely transferred was obtained. In addition, the height of the part with the concave pattern of the hardened concrete concave pattern is lower than the height defined by the dimensions of the formwork by the thickness of the sheet-like base material, and a product almost as specified is obtained. It was.
[0061]
【Example1]
  [Prepolymer production]
  A 1-L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. After adding 9 parts by weight and reacting at 80 ° C. for about 3 hours, 3.3 parts by weight of 2-methacryloyloxyisocyanate is added, and further reacted for about 3 hours. A prepolymer b having a number average molecular weight of about 10,000 was produced, with an average of about 2 polymerizable unsaturated groups per molecule. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.
[0062]
[Adjustment of photosensitive resin composition]
For 70 parts by weight of the prepolymer b, 10 parts by weight of benzyl methacrylate, 10 parts by weight of cyclohexyl methacrylate, 10 parts by weight of diethylene glycol monobutyl ether monomethacrylate, 0.4 weight of 2,2-dimethoxy-2-phenylacetophenone photopolymerization initiator Parts, polymerization inhibitor 2,6-t-butyl-4-methylphenol 0.05 parts by weight, and fine powder silica having a number average particle size of 4.5 μm (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “Syrosphere C- 1504 ") 5 parts by weight were mixed to obtain a photosensitive resin composition B.
[0063]
  [Preparation of resin plate]
  Except for using a laminate film made of an entirely transparent polyester film having a thickness of 150 μm instead of a negative film,referenceIn the same manner as in Example 1, a sheet-like laminate was formed in which a cured product layer having a thickness of 2.5 mm consisting essentially of only a convex pattern of the photosensitive resin composition was laminated on the surface of the sheet-like substrate. However, since the entire surface of the photosensitive resin composition layer is exposed, it is not necessary to remove the uncured portion.
[0064]
Next, using a carbon dioxide laser engraving machine, a convex pattern was formed on the photosensitive resin cured product layer of the sheet-like laminate by digging up to the place where the sheet-like substrate was exposed. The laser engraving machine used was a trade mark “TYP STAMPLAS SN 09” manufactured by BAASEL. In this apparatus, a laser beam can be computer-controlled to form a pattern on the cured photosensitive resin layer faithfully according to CAD data.
Through the above-described steps, a resin plate for concrete mold (I) in which a convex pattern was formed on the surface of the sheet-like substrate was produced.
The thickness of the remaining resin layer remaining in the portion other than the convex pattern on the surface of the sheet-like substrate was 10 μm or less, and this value was 0.4% or less of the height of the convex pattern.
[0065]
[Paste to concrete formwork]
A spray-type adhesive was applied to the surface of the resin mold (a) for concrete mold obtained as described above where the convex pattern was not present, and was stuck to an iron concrete mold.
[0066]
[Transfer of pattern to concrete surface]
Poured ready-mixed concrete consisting of 100 parts by weight of Pordoland cement, 200 parts by weight of sand, 300 parts by weight of gravel and 60 parts by weight of water in a mold, heated in a steam bath at 70-75 ° C. for 4 hours, and then at room temperature. The concrete was hardened by cooling for 30 minutes. Hardened concrete is easily released from the metal formwork, and the resulting concrete surface is smooth and free of any deposits. The photosensitive resin applied in the formwork is also completely on the formwork surface. It remained attached. On the surface of the hardened concrete, a concave pattern in which the convex pattern of the resin plate was completely transferred was obtained. Moreover, the height of the part with the concave pattern of the hardened concrete was only lower by the thickness of the sheet-like base material than the height defined by the dimensions of the mold, and a product almost according to the standard was obtained.
[0067]
[referenceExample2]
  [Preparation of resin form for concrete formwork]
  Except for using a wholly aromatic polyamide film having a thickness of 50 μm (made by Asahi Kasei Co., Ltd., trade name “Aramika”) as a sheet-like substratereferenceIn the same manner as in Example 1, a concrete mold resin plate (c) was prepared. The surface of the wholly aromatic polyamide film used as the sheet-like substrate is subjected to plasma treatment in order to improve the adhesion with the substrate to be laminated, and an epoxy adhesive having a thickness of several μm is provided on one side of the film. A layer was formed. Moreover, the linear thermal expansion coefficient of the wholly aromatic polyamide film was 4 ppm / ° C. Furthermore, the heat distortion temperature was 250 ° C. or higher.
  The thickness of the remaining resin layer remaining in the portion other than the convex pattern on the surface of the sheet-like substrate was 10 μm or less, and this value was 0.4% or less of the height of the convex pattern.
[0068]
[Paste to concrete formwork]
A double-sided adhesive tape was affixed to the surface of the resin plate for concrete mold (c) produced as described above where the convex pattern was not formed, and affixed to the iron concrete mold.
[0069]
[Transfer of pattern to concrete surface]
Poured ready-mixed concrete consisting of 100 parts by weight of Pordoland cement, 200 parts by weight of sand, 300 parts by weight of gravel and 60 parts by weight of water in a mold, heated in a steam bath at 70-75 ° C. for 4 hours, and then at room temperature. The concrete was hardened by cooling for 30 minutes. Hardened concrete is easily released from the metal formwork, and the resulting concrete surface is smooth and free of any deposits. The photosensitive resin applied in the formwork is also completely on the formwork surface. It remained attached. On the surface of the hardened concrete, a concave pattern in which the convex pattern of the resin plate was completely transferred was obtained. In addition, the height of the part with the concave pattern of the hardened concrete is only as low as the thickness of the sheet-like base material from the height specified by the dimensions of the mold, and a product almost in accordance with the standard was obtained. .
[0070]
【Example2]
  [Preparation of resin form for concrete formwork]
  Example1By the same method, a resin plate for concrete formwork (I) was produced. The surface of the resin plate was modified by treating it with a silane coupling agent having a perfluoroalkyl group. Silane coupling agent treatment by stirring 10 g of a perfluoroalkyl group-containing silane coupling agent (trademark “TSL8233” manufactured by GE Toshiba Silicone), 939 g of methanol, 1 g of acetic acid, and 50 g of water at room temperature (25 ° C.) for 1 hour. A liquid was obtained. This treatment liquid was applied uniformly and thinly on the surface of the resin mold for concrete formwork, and dried at 100 ° C. for 10 minutes. Thus, a resin plate (d) for concrete mold was obtained.
  The thickness of the remaining resin layer remaining in the portion other than the convex pattern on the surface of the sheet-like substrate was 10 μm or less, and this value was 0.4% or less of the height of the convex pattern.
[0071]
[Paste to concrete formwork]
A double-sided adhesive tape was affixed to the surface of the concrete mold resin plate (d) produced as described above where the convex pattern was not formed, and affixed to the iron concrete mold.
[0072]
[Transfer of pattern to concrete surface]
Poured ready-mixed concrete consisting of 100 parts by weight of Pordoland cement, 200 parts by weight of sand, 300 parts by weight of gravel and 60 parts by weight of water in a mold, heated in a steam bath at 70-75 ° C. for 4 hours, and then at room temperature. The concrete was hardened by cooling for 30 minutes. Hardened concrete is easily released from the metal formwork, and the resulting concrete surface is smooth and free of any deposits. The photosensitive resin applied in the formwork is also completely on the formwork surface. It remained attached. On the surface of the hardened concrete, a concave pattern in which the convex pattern of the resin plate was completely transferred was obtained. In addition, the height of the part with the concave pattern of the hardened concrete is only as low as the thickness of the sheet-like base material from the height specified by the dimensions of the mold, and a product almost in accordance with the standard was obtained. .
[0073]
When a test was performed in which the surface of the concrete taken out from the mold was hammered with a hammer, several recesses less than 1 mm occurred on the surface, but no cracks or the like occurred. The material of the hammer used was steel, the surface to be downed was flat, circular with a diameter of about 50 mm, and the weight was about 2 kg. The same location on the concrete surface was struck 5 times by dropping the hammer from its height of about 30 cm with its own weight without applying force.
[0074]
In addition, a steel ball having a diameter of 10.9 mm and a weight of 5.4 g was dropped from a height of 30 cm onto the concrete surface, and the height at which the steel ball was repelled was measured to be 10 cm.
Furthermore, the metal mold was repeatedly used without applying the mold release agent. However, the mold could still be released smoothly after repeated use, and the surface of the obtained concrete was smooth. There was no deposit.
Furthermore, it was found that rust does not occur on the surface of the formwork and has a rust prevention effect.
[0075]
【Example3]
  Example1The same photosensitive resin composition B was prepared, and the photosensitive resin cured product layer having an average thickness of 0.2 mm was left without digging with a carbon dioxide laser until the surface of the sheet-like substrate was exposed. By the way, except for stopping laser processing1In the same manner as above, a resin plate having a convex pattern formed on the surface of a sheet-like substrate was produced. That is, a convex pattern having a height of about 2.3 mm is formed on the surface of a sheet-like base material having a thickness of 180 μm with an adhesive layer of several μm on the surface, and a concave portion other than the convex pattern portion is formed. The bottom is a resin plate in which a photosensitive resin cured product layer remains with an average value of 0.2 mm. The thickness of the resin residual layer was 8.7% of the height of the convex pattern.
[0076]
  Next, the example2In the same manner as described above, the surface of the resin plate on which the convex pattern was present was treated with a silane coupling agent having a perfluoroalkyl group to obtain a resin plate for concrete form (e).
  Furthermore,referenceIn the same manner as in Example 1, the resin plate (e) was attached to the concrete mold surface, and the pattern of the resin plate surface was transferred to the concrete surface.
  Hardened concrete is easily released from the metal formwork, and the resulting concrete surface is smooth and free of any deposits. The photosensitive resin applied in the formwork is also completely on the formwork surface. It remained attached. On the surface of the hardened concrete, a concave pattern in which the convex pattern of the resin plate was completely transferred was obtained. Further, the height of the portion having the concave pattern of the hardened concrete is equal to the thickness defined by the dimensions of the formwork, the thickness of the sheet-like base material, and the thickness of the remaining photosensitive resin cured product layer, that is, 0. The product was only 38 mm lower, and a product almost in accordance with the standard was obtained.
[0077]
When a test was performed in which the surface of the concrete taken out from the mold was hammered with a hammer, several recesses less than 1 mm occurred on the surface, but no cracks or the like occurred. The material of the hammer used was steel, the surface to be downed was flat, circular with a diameter of about 50 mm, and the weight was about 2 kg. The same location on the concrete surface was struck 5 times by dropping the hammer from its height of about 30 cm with its own weight without applying force.
[0078]
In addition, a steel ball having a diameter of 10.9 mm and a weight of 5.4 g was dropped from a height of 30 cm onto the concrete surface, and the height at which the steel ball was repelled was measured to be 10 cm.
Furthermore, the metal mold was repeatedly used without applying the mold release agent. However, the mold could still be released smoothly after repeated use, and the surface of the obtained concrete was smooth. There was no deposit.
Furthermore, it was found that rust does not occur on the surface of the formwork and has a rust prevention effect.
[0079]
[Comparative Example 1]
A natural rubber plate having a thickness of 4 mm was placed on a mold having a pattern formed on the surface thereof, and heat-pressed to transfer the mold pattern onto the natural rubber plate. The height of the convex pattern of the rubber plate to which the pattern was transferred was 2.5 mm, and the thickness of the base portion, that is, the portion without the pattern was 1.5 mm. Further, as a result of measuring the thickness at the convex pattern portion, the thickness was partially uneven, and the plate thickness accuracy was about ± 0.2 mm. This is presumably because the rubber composition is difficult to fluidize during hot pressing.
[0080]
[Paste to concrete formwork]
A double-sided adhesive tape was affixed to the surface of the natural rubber plate produced as described above where the convex pattern was not formed, and affixed to an iron concrete formwork.
[0081]
[Transfer of pattern to concrete surface]
A release agent made of mineral oil is applied to the surface of the rubber plate, and ready-mixed concrete made of 100 parts by weight of Pordoland cement, 200 parts by weight of sand, 300 parts by weight of gravel, and 60 parts by weight of water is poured into the mold. After heating in a steam bath at 75 ° C. for 4 hours, the concrete was cured by cooling at room temperature for 30 minutes.
A concave pattern in which the convex pattern of the rubber plate was transferred was obtained on the hardened concrete surface. Also, the height of the part with the concave pattern of the hardened concrete is as low as 1.5 mm, which is the thickness of the base of the rubber plate, from the height specified by the dimensions of the mold, which is said to be in accordance with the standard It became a hard product.
The hardened concrete had a very poor release property from the metal mold, and at the time of release, a part of the molded concrete was lost or the concrete adhered to the mold.
[0082]
  Example2In the same manner as described above, a test in which the surface of the concrete taken out from the mold was hit with a hammer was performed. As a result, innumerable recesses with a depth of several mm were generated, and cracks were also confirmed.
  In addition, a steel ball having a diameter of 10.9 mm and a weight of 5.4 g was dropped from a height of 30 cm onto the concrete surface, and the height at which the steel ball was repelled was measured to be 4 cm.
[0083]
[Comparative Example 2]
  Other than using a polyethylene film having a linear thermal expansion coefficient of 150 ppm / ° C., a melting temperature of 135 ° C. and a thickness of 150 μm as the sheet-like substrate,referenceIn the same manner as in Example 1, a concrete mold resin plate (f) was produced.
[0084]
[Paste to concrete formwork]
A double-sided adhesive tape was affixed to the surface of the concrete mold resin plate (f) prepared as described above where the convex pattern was not formed, and affixed to the iron concrete mold.
[0085]
[Transfer of pattern to concrete surface]
A release agent made of mineral oil is applied to the surface of the rubber plate, and ready-mixed concrete made of 100 parts by weight of Pordoland cement, 200 parts by weight of sand, 300 parts by weight of gravel, and 60 parts by weight of water is poured into the mold. After heating in a steam bath at 75 ° C. for 4 hours, the concrete was cured by cooling at room temperature for 30 minutes.
A concave pattern obtained by transferring the convex pattern of the resin plate was obtained on the cured concrete surface. However, the resin plate was deformed during hardening of the concrete, and the convex pattern was not faithfully transferred. The deviation from the design position of the pattern estimated to be due to deformation of the resin plate was several mm at a large place. Moreover, the surface of the hardened concrete had a part which became depressed, and there was a problem in the uniformity of height.
[0086]
[Comparative Example 3]
  Except that the minimum dimension of the black shading part of the negative film is 0.2 mm,referenceA concrete resin plate (ki) was obtained in the same manner as in Example 1. In this resin plate (ki), the thickness of the resin residual layer remaining in the portion other than the convex pattern on the surface of the sheet-like substrate at the portion corresponding to the minimum dimension of 0.2 mm of the light shielding portion of the negative film is 1 0.5 mm, which was 60% of the height of the convex pattern. However, in the part where the dimension of the light shielding part is larger than 3 mm, the thickness of the resin residual layer is 10 μm or less, and this value is 0.4% or less of the height of the convex pattern. Therefore, in the light shielding part of the negative film, a large difference in the thickness of the residual resin layer occurred between the small dimension part and the large dimension part.
[0087]
[Paste to concrete formwork]
A double-sided adhesive tape was affixed to the surface of the concrete mold resin plate (f) prepared as described above where the convex pattern was not formed, and affixed to the iron concrete mold.
[0088]
[Transfer of pattern to concrete surface]
A mold release agent made of mineral oil is applied to the surface of the rubber plate, and ready-mixed concrete made of 100 parts by weight of Pordoland cement, 200 parts by weight of sand, 300 parts by weight of gravel and 60 parts by weight of water is poured into the mold. After heating in a steam bath at 75 ° C. for 4 hours, the concrete was cured by cooling at room temperature for 30 minutes.
The pattern of the resin plate (ki) was faithfully transferred on the surface of the concrete taken out from the mold, but there is a big difference in the depth of the recessed part transferred to the concrete side depending on the size of the light shielding part of the negative film. This was a deviation from the standard of the designed dimensions.
[0089]
【The invention's effect】
According to the present invention, the dimensional accuracy is high, the releasability is excellent, the concave and convex pattern obtained by faithfully copying the pattern of the resin plate can be formed on the surface of the concrete, and it can be used repeatedly, has excellent durability, and is hardened. It is possible to provide a resin plate for a concrete mold with high dimensional stability and a method for forming the same, which has a hard surface and can shorten the period until it is completely cured after being taken out from the mold.
[Brief description of the drawings]
[Figure 1]referenceIt is a figure which shows the preparation methods of the resin plate of an example, (a), (b), (c) and (d) are explanatory drawings which show a preparation procedure.
FIG. 2 is a cross-sectional view showing a conventional resin plate for concrete formwork.
FIG. 3 is a cross-sectional view illustrating a taper angle of a convex pattern formed on the surface of a sheet-like substrate.
[Explanation of symbols]
1 Sheet-like substrate
2 Photosensitive resin composition layer
3 Negative film
4 Cured product of photosensitive resin composition
W The thickness of the base of the conventional resin plate
R Taper angle of convex pattern

Claims (3)

  A resin plate comprising a sheet-like base material and a photosensitive resin cured product layer having a convex pattern formed by laser engraving, which is used by being mounted on the surface of a concrete mold, wherein the sheet-like base material has a thickness of 0. 01 mm or more and 1 mm or less and a linear thermal expansion coefficient of 100 ppm / ° C. or less, and the cured photosensitive resin contains (A) a plurality of polycarbonate diol segments bonded via urethane bonds, and at least one terminal is not ethylenically A cured product of a photosensitive resin composition comprising an unsaturated polyurethane prepolymer having a saturated group, (B) a reactive monomer having at least one polymerizable reactive group, and (C) a photopolymerization initiator, The convex pattern of the cured photosensitive resin has a height of 0.01 mm or more and 50 mm or less, and the thickness of the remaining resin layer in the portion where the convex pattern does not exist is convex. Concrete formwork resin plate is 10% or less of the pattern.   A concrete mold in which the resin plate according to claim 1 is mounted on the surface of a concrete mold via an adhesive layer. Unsaturated polyurethane prepolymer having a plurality of polycarbonate diol segments bonded via (A) urethane bonds to the surface of a sheet-like substrate having a thickness of 0.01 mm or more and 1 mm or less and having an ethylenically unsaturated group at at least one end (B) A liquid photosensitive resin composition layer containing at least one reactive monomer having a polymerizable reactive group and (C) a photopolymerization initiator is provided, and high energy rays are provided on the entire surface of the liquid photosensitive resin layer. The photosensitive resin layer is cured by irradiation, and further the photosensitive resin cured product layer is removed by irradiating with a laser, whereby the photosensitive material having a height of 0.01 mm or more and 50 mm or less on the sheet-like substrate. A convex pattern of the cured resin product is formed, and the thickness of the resin residual layer where the convex pattern does not exist is 10% or less of the convex pattern. Method for producing a concrete formwork for resin plate to.

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