JP3964253B2 - Resin plate for concrete formwork - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin plate for protecting the surface of a concrete formwork or a resin plate for imparting an uneven pattern to the concrete surface.
[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. A method of transferring the pattern to a rubber plate, or JP-A-3-63354 discloses a method of producing a resin plate having a concavo-convex pattern using photolithography.
[0003]
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. It is also described in Japanese Patent Application Laid-Open No. 60-101007 that the releasing agent inhibits the hardening of the concrete surface.
[0004]
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. Furthermore, since the surface is contaminated with stains due to the mold release agent, the appearance is lost due to discoloration, and when the appearance is required, there is a problem that a process of repairing the surface is required.
[0005]
[Problems to be solved by the invention]
In order to solve the above problems, the present invention provides a resin plate for concrete formwork that is excellent in releasability, has a hard hardened concrete surface, and can shorten the period until it is completely cured after being taken out of the formwork and its formation Is to provide a method.
[0006]
[Means for Solving the Problems]
As a result of intensive studies, the inventors have been able to easily remove the concrete cured by heat curing from the mold by using a resin plate having an amino group on the surface, and the concrete immediately after being removed from the mold The present inventors have found that the surface is very hard and that a period until the resin is completely cured can be greatly shortened, and that a surprising effect that cannot be considered at all in the conventional resin plate appears, and the present invention has been completed. That is, the present invention is as follows.
[0007]
1. A resin plate that is used by being mounted on the surface of a concrete formwork, wherein an amino group having active hydrogen is present on the surface, and when the surface amino group is measured using X-ray photoelectron spectroscopy (XPS method) The ratio of the number of nitrogen atoms to the number of carbon atoms is from 0.1 atomic% to 20 atomic%, and the resin plate for concrete formwork.
2. 1. A resin plate has a convex pattern produced by curing a photosensitive resin composition by irradiating high energy rays. The resin plate for concrete molds as described.
[0008]
3. The photosensitive resin composition is essential for (A) a prepolymer having a number average molecular weight of 1,000 to 500,000, (B) a reactive monomer having a polymerizable reactive group having a molecular weight of less than 1000, and (C) a photopolymerization initiator. As a component, the component (A) or (B) contains 1 to 70 wt% of the total weight of (A) and / or (B) the compound (D) in which an amino group having active hydrogen is present in the molecule, (A) 5 to 200 parts by weight of component (B) with respect to 100 parts by weight, and 0.1 to 10% by weight of component (C) with respect to the total weight of components (A) and (B) 2. The resin plate for concrete molds as described.
[0009]
4). The component (A) of the photosensitive resin composition is an unsaturated polyurethane prepolymer having a plurality of diol segments bonded through urethane bonds and having an ethylenically unsaturated group at least at one end, and the component (B) is 2. a reactive monomer having at least one ethylenically unsaturated bond; The resin plate for concrete molds as described.
5). Furthermore, it contains a filler having a hydroxyl group on the surface having a number average particle diameter of 0.01 μm or more and 100 μm or less. The resin plate for concrete molds as described.
[0010]
6). Non-photosensitive resin composition, or prepolymer and / or reactive monomer component in which raw material of resin plate contains 5 to 50 wt% of polymer containing 1 to 50% of monomer having amino group of all monomer units 1. Use a photosensitive resin composition containing 1 to 70 wt% of a polymerization reactive compound having an amino group therein. The manufacturing method of the resin plate of description.
7). 1. a step of treating the resin plate surface with a treatment liquid containing a compound containing an amino group and fixing the amino compound to the resin plate surface; The manufacturing method of the resin plate for concrete molds of description.
[0011]
8). 1. The resin plate is a resin plate having a convex pattern on the surface, and the method of forming the convex pattern is a method of removing the resin by irradiating a laser. A method for forming a resin plate for concrete formwork as described.
9. 1. Plasma treatment of the surface of the resin plate in a gas containing a nitrogen-containing compound A method for forming a resin plate for concrete formwork as described.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described with a focus on preferred embodiments.
The resin plate for concrete mold of the present invention has an amino group having active hydrogen on the surface, particularly the surface in contact with concrete, and a method for quantifying the amount of the amino group present is an X-ray photoelectron. Spectroscopic method (XPS method). This method is a method for identifying elements present on the sample surface by irradiating the sample surface with X-rays and measuring the kinetic energy of photoelectrons leaving the surface. The feature of this method is that it can obtain information on the surface near several nanometers and can observe the chemical state of the element. For example, in the case of a carbon atom, the kinetic energy of the photoelectron obtained differs depending on the type of atom adjacent to the carbon atom, so whether it is carbon derived from a carbonyl group, carbon derived from an ethylenically unsaturated group, carbon derived from an alkyl group, etc. Can be determined. However, when focusing on nitrogen atoms derived from amino groups, there is little difference in photoelectron kinetic energy to distinguish them from urethane-bonded nitrogen, urea-bonded nitrogen, etc. The abundance of amino groups cannot be quantified. Therefore, using a labeled compound that reacts specifically with an amino group, this labeled compound reacts with the amino group on the sample surface, and the element in the labeled compound is identified to quantify the surface amino group. it can. As a labeling compound to be used, a generally used compound can be used. For example, pentafluorobenzaldehyde introduced in Analytical Chemistry, Vol. 53, No. 4, 669 (1981) or Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 26, 559-572 (1988). And the element of interest is fluorine. This labeling compound reacts with primary amines or secondary amines having active hydrogen, but does not react with amide compounds, imide compounds, nitrile compounds, nitrogen-containing heterocyclic compounds, urethane compounds, and urea compounds.
[0013]
Next, how to determine the ratio of the number of nitrogen atoms derived from an amino group to the number of carbon atoms will be described. Since one molecule of the labeling compound pentafluorobenzaldehyde reacts with one amino group, the spectrum intensity I (F) derived from a fluorine atom is reduced to 1/5, and the value of carbon atom The value obtained by taking the ratio with the spectral intensity I (C) and further correcting with the relative sensitivity coefficient of the fluorine atom and the carbon atom is the ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms. A relative sensitivity coefficient is a numerical value peculiar to a measuring apparatus, and is calculated | required by measuring a known composition on the same conditions as a sample.
[0014]
The ratio of the number of nitrogen atoms derived from amino groups present on the surface of the resin plate for concrete molds of the present invention to the number of carbon atoms is from 0.1 atomic% to 20 atomic%. A more preferable range is 0.1 atomic percent or more and 10 atomic percent or less. When the content is less than 0.1 atomic%, the effect of improving the curability of the concrete surface is low. When the content exceeds 20 atomic%, the hygroscopicity and swelling are increased, or the resin is easily dissolved in an aqueous solution. The plate surface is altered and the dimensions of the convex pattern are likely to change.
[0015]
The resin plate for concrete molds of the present invention is a method in which a resin plate having a convex pattern formed on its surface is attached to a concrete mold using an adhesive or the like, and a concave pattern corresponding to the convex pattern is transferred to the concrete surface. It can be used for the purpose of forming and imparting design properties, and for the purpose of protecting the mold by attaching a resin plate having no convex pattern to the surface of the concrete mold.
[0016]
A method of forming a convex pattern on the surface of a resin plate is produced by forming a photosensitive resin layer on a sheet-like substrate and processing it using photolithography to cure the photosensitive resin layer by irradiating high energy rays. Surface of the mold by hot pressing a mold produced using photolithography and a thermoplastic resin plate, a thermosetting resin plate, or a rubber plate such as natural rubber, silicon rubber, etc. that is fluidized by heating This method is generally used such as a method of transferring a convex pattern, a method of engraving a resin plate or a rubber plate manually or automatically using a blade or a grinding tool, and a method of engraving a resin plate by irradiating it with a laser. You can use that method. In the convex pattern on the surface of the resin plate, the height of the convex portion is preferably 10 μm or more and 50 mm or less. The thickness is preferably 10 μm or more from the viewpoint of the design of the concrete surface pattern and 50 mm or less from the viewpoint of easy removal from the formwork of the hardened concrete.
[0017]
The sheet-like base material used in photolithography is preferably a material having high dimensional stability. A desirable range of linear thermal expansion coefficient is 100 ppm / ° C. or less, preferably 60 ppm / ° C. or less, and more preferably 50 ppm / ° C. or less.
In photolithography, a high energy beam from a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a laser, etc. is irradiated to cure the portion hit by the high energy beam, followed by a development process to remove the uncured portion. Go through. In the development step, a method of spraying or immersing the treatment liquid capable of dissolving or dispersing the uncured resin in the treatment liquid, a method of removing the uncured part by irradiating high-pressure steam, or applying heat to the resin plate and sponge For example, a method of melting the uncured portion with a sheet-like sheet and removing it by adsorption can be used.
[0018]
In the method of ablating and melting and removing the resin by irradiating laser light, a convex pattern can be formed directly without going through a development process. Examples of the laser to be used include those having an oscillation wavelength in the infrared region such as a carbon dioxide laser and a YAG laser, and those having an oscillation wavelength in the ultraviolet region such as the third and fourth harmonics of the YAG laser and an excimer laser. .
[0019]
The prepolymer having a number average molecular weight of 1,000 or more and 500,000 or less, which is an essential component (A) constituting the photosensitive resin composition according to claim 3 of the present invention, is not particularly limited. Unsaturated polyurethane, polyurethane resin, polyester resin, unsaturated polyester resin, polyimide resin, polysulfone resin, polyamide resin, polycarbonate resin, etc. as polymers, polyolefins such as polystyrene resin, polyethylene resin, polypropylene resin as addition polymerization prepolymers, Polybutadiene resins such as homopolymers or copolymers, and ring-opening polymerization prepolymers include epoxy resins and polysiloxane resins alone or copolymers. In the case of a prepolymer having a number average molecular weight of less than 1000, the viscosity of the composition can be lowered, but it is difficult to ensure the mechanical properties of the cured product formed by irradiation with high energy rays. When removing the product in the development step, it is difficult to dissolve or disperse in the developer. A more preferable range of the number average molecular weight is 2000 or more and 200,000 or less, and particularly preferably 2000 or more and 100,000 or less. Moreover, the prepolymer which has a polymerizable reactive group in a molecule | numerator can also be used. The method for measuring the number average molecular weight of the prepolymer of the present invention is gel permeation chromatography (GPC) using polystyrene as a standard.
[0020]
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.
[0021]
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, polycarbonate diols, and the like.
[0022]
The molecular weight determined from the hydroxyl value of the diol compound is preferably 400 to 5000, but it is more preferable to use a molecular weight of about 500 to 2500 from the viewpoint of obtaining a more flexible and strong polyurethane.
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.
[0023]
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.
[0024]
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.
[0025]
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.
[0026]
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.
[0027]
Furthermore, polar groups such as carboxyl groups can be introduced into the unsaturated polyurethane. The introduction of a carboxyl group into an unsaturated polyurethane is, for example, by adding an ethylenically unsaturated compound containing two hydroxyl groups to a polyurethane having both end isocyanate groups, and reacting one of the hydroxyl groups with an isocyanate group to react with the hydroxyl group. An unsaturated polyurethane having two ethylenically unsaturated bonds and an acid anhydride is added to cause a ring-opening reaction with the hydroxyl groups of the polyurethane, so that a carboxyl group and an ethylenically unsaturated bond are simultaneously formed at both ends. It can be an unsaturated polyurethane.
[0028]
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.
[0029]
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.
[0030]
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.
[0031]
The reactive monomer having a polymerizable reactive group according to claim 3 of the present invention is a monomer having an ethylenically unsaturated group such as a vinyl group, an acrylic group or a methacrylic group, a cyclic ether such as an epoxy or oxetane, a cyclic group Examples thereof include monomers having a ring-opening polymerizable reactive group such as carbonate, lactone, lactam, and cyclic acetal. 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.
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.
[0032]
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.
[0033]
Further, 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 has 1 or more, preferably 2 or more ring-opening polymerizable reactive groups in the molecule.
[0034]
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 in which ethylene oxide or propylene oxide is added 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.
[0035]
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.
[0036]
Examples of the photopolymerization initiator according to claim 3 of the present invention include a photo radical generator, a photo acid generator, a photo base generator and the like.
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 -Oxycarbonyl) benzophenone, dibenzosuberone, 2-ethylanthraquinone, triethanolamine, methyldiethanolamine, triisopropanolamine, Michlerketone, 4,4'-diethylaminophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (N-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid.
[0037]
As a specific example of the photoacid generator, BF is used as a counter ion. _Four -Or PF ₆ -SbF ₆ A 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 act to generate a curing reaction by generating acids such as Lewis acid and Bronsted acid by irradiation of actinic radiation. From the viewpoint of curability, triarylsulfonium salts are preferred. Of these, triarylsulfonium hexafluorophosphate is excellent in terms of thick film curability.
[0038]
Photobase generators include oxime ester compounds that generate Schiff bases upon irradiation with high energy rays, ammonium compounds that generate amines, dimethoxybenzyl urethane compounds, benzoin compounds, orthonitrobenzyl urethane compounds, hydroxy ions Can be used. Moreover, the photobase generator described in the publication of published patent 2000-330270 can also be used.
[0039]
It is preferable that the photoinitiator used by this invention contains 0.1-10 wt% with respect to the total weight of a prepolymer component (A) and a reactive monomer component (B). It is preferably 0.1 wt% or more in terms of sufficient curing, and 10 wt% or less in terms of mechanical properties of the cured product.
In the present invention, the resin plate preferably contains a filler having a number average particle size of 0.01 μm to 100 μm, more preferably 0.1 μm to 50 μm, and still more preferably 0.5 μm to 20 μm. Can do. From the viewpoint of suppressing an extreme increase in viscosity and thixotropy of the resin composition, it is preferably 0.01 μm or more, and 100 μm or less in order not to make excessive irregularities on the surface.
[0040]
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, phosphates, etc. Inorganic pigments, carbon black, gold, silver, copper, platinum, palladium, nickel, aluminum, silicon, brass, or other simple metals or alloy powders, or metal powders coated with dissimilar metals, organic compounds Examples thereof include colored fillers in which pigments or dyes are dispersed in fine particles.
[0041]
In particular, a filler having a hydroxyl group on the surface is preferable. 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. The filler having a hydroxyl group has high adhesion to the resin, and a silane coupling agent having an amino group can be reactively fixed to the surface hydroxyl group of the filler exposed on the surface of the resin plate.
In addition, when the particle size distribution is wide, the filling rate increases when the colorant is contained at a high concentration, so that the permeability of the active ray is lowered. The shape of the filler 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.
[0042]
The content of the filler used in the present invention is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 20 parts by weight or less with respect to 100 parts by weight of the resin composition. From the viewpoint of curability inside the resin plate, 50 parts by weight or less is preferable.
In addition, by including the organic fine particles, particularly fluorine fine particles such as tetrafluoroethylene, it is possible to improve releasability from concrete. Furthermore, wear resistance can also be improved by containing ceramic fine particles such as boron nitride, silicon nitride and silicon carbide.
[0043]
Moreover, the photosensitive resin composition of this invention can also contain a pigment | dye, and can also adjust the transmittance | permeability of a high energy ray. As pigments to be added, organic pigments such as phthalocyanines, quinacridones, isoindolinones, perinones, dioxazines, or azo dyes, anthraquinone dyes, indigoid dyes, triphenylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, And dyes such as cyanine pigments.
[0044]
An example of a method for introducing an amino group on the surface of the resin plate in the present invention will be described. Here, the surface means at least a part of the entire surface, and particularly refers to a surface in contact with concrete.
First, the first method is a method of adding a compound containing an amino group to a resin composition when producing a sheet-shaped resin plate. In this method, it is necessary to add a compound having an amino group to such an extent that the amino group is exposed on the surface of the resin plate, and it is necessary to devise so that the amino group does not leave. In the case of a resin composition having no photosensitivity, the monomer unit constituting the polymer may contain a polymer containing an amino group-containing monomer in an amount of 1 to 50% of the total monomer unit in an amount of 5 to 50 wt% of the total polymer weight. preferable. In this method, a method in which a polymer is dissolved in a solvent and applied, and then the solvent is dried and removed, or a method in which the polymer is melted by heating to form a sheet is taken.
[0045]
In the case of a photosensitive resin composition having the property of being cured by irradiation with high energy rays, the polymerization reactivity having an amino group in the prepolymer component and / or reactive monomer component constituting the photosensitive resin composition. A compound containing 1 to 70 wt%, preferably 5 to 50 wt%, more preferably 10 to 40 wt%, and curing the photosensitive resin composition by irradiation with high energy rays, and at the same time polymerization reaction having an amino group This is a method of immobilizing a compound in a cured product. When the prepolymer or reactive monomer having an amino group exceeds 70 wt%, the hydrophilicity of the resin plate is increased and the resin plate is easily dissolved or swelled in an aqueous solution. Therefore, the resin plate swells or dissolves when it comes into contact with ready-mixed concrete containing a large amount of moisture. Moreover, when it is less than 1 wt%, the density | concentration of the amino group exposed on the surface is low, and the effect of accelerating the curability of concrete is low. Reactive monomers having an ethylenically unsaturated group are preferred, and specific examples include allylamine, vinylethylamine, allylmethylamine, o-aminostyrene, m-aminostyrene, p-aminostyrene, p-amino-α-methylstyrene, m-amino-α-methylstyrene, o-amino-α-methylstyrene, 2-aminoethyl (meth) acrylate, 2-methylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-aminoethyl (Meth) acrylate, 3-aminopropyl (meth) acrylate, 2-methylaminopropyl (meth) acrylate, 3-methylaminopropyl (meth) acrylate, N- (2-aminoethyl) (meth) acrylamide, N- ( 3-methylaminopropyl) (meth) acrylami , It may be mentioned vinyl piperidine, vinyl piperazine, vinyl amine, a low molecular compound such as vinyl methyl amine.
[0046]
As a method for introducing an amino group into the prepolymer, a method in which the prepolymer having an ethylenically unsaturated group in the molecular chain is reacted with the polymerization reactive monomer having an amino group, or a prepolymer having a hydroxyl group in the molecular chain is used. A method of reacting an amino group-containing silane coupling agent or a titanium coupling agent with a polymer, a method of adding a compound having a plurality of amino groups to a prepolymer having an isocyanate group or an epoxy group in the molecular chain, and reacting them. Etc. In addition, a natural polymer having an amino group such as chitosan or a derivative obtained by reacting a compound having an ethylenically unsaturated bond with a hydroxyl group in the molecule while protecting the amino group of chitosan can be used.
[0047]
In the present invention, the second method for introducing an amino group to the resin plate surface is to apply a treatment liquid containing a compound containing an amino group to the resin plate surface, and to introduce an ethylenically unsaturated group or hydroxyl group present on the resin plate surface. In this method, the amino compound is reacted with an ethylenically unsaturated group or a reactive group such as an ethoxysilyl group, a methoxysilyl group, or a trichlorosilyl group. The compound containing an amino group is an amino compound having an ethylenically unsaturated group, a coupling agent such as a silane coupling agent or a titanium coupling agent having an amino group, a compound having a hydroxyl group and an amino group at the same time, an amino group And the like. Examples of the silane coupling agent having an amino group include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ. Mention may be made of aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane. Examples of the titanium coupling agent having an amino group include isopropyl tri (N-aminoethyl-aminoethyl) titanate. These compounds react with hydroxyl groups on the surface of the resin plate. Examples of a method for introducing a hydroxyl group into the surface of the resin plate include a method of mixing a compound having a hydroxyl group in the resin forming the resin plate, a method of generating a hydroxyl group by post-treating the surface of the resin plate.
[0048]
The coupling agent treatment method in the present invention 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, a brush coating method, or the like 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. The hydroxyl group on the surface of the resin plate is derived from an organic compound constituting the resin, or derived from a filler in the resin plate.
[0049]
In the case of an amino compound having an ethylenically unsaturated group, a photoradical generator is added to the treatment liquid, and irradiation with high energy rays causes a photopolymerization reaction with the ethylenically unsaturated group present on the surface of the resin plate to fix. Can be
When the resin plate surface has an isocyanate group, the amino compound can be immobilized on the resin plate surface by reacting the isocyanate group with one amino group of a compound having a plurality of amino groups. As a method for introducing an isocyanate group on the surface of the resin plate, a resin introduced by a method of mixing a compound having a hydroxyl group in the resin forming the resin plate, a method of generating a hydroxyl group by post-treating the surface of the resin plate, etc. The method of making the hydroxyl group of a plate surface and a diisocyanate compound react can be mentioned. By these methods, a resin plate having an isocyanate group exposed on the surface can be formed.
[0050]
In addition, when the resin plate surface has a carboxyl group, the amino compound can be immobilized on the resin plate surface by subjecting one amino group of the compound having a carboxyl group and a plurality of amino groups to a dehydration condensation reaction. . Examples of a method for introducing a carboxyl group into the resin plate surface include a method of mixing a compound having a carboxyl group in the resin forming the resin plate, a method of generating a carboxyl group by post-treating the resin plate surface, and the like. Can do.
[0051]
As a method for generating a hydroxyl group or a carboxyl group on the surface of the resin plate, there is a method of irradiating the surface of the resin plate with active energy rays. The irradiation of the active energy ray is preferably performed before the treatment liquid having amino groups is applied to the resin plate surface. The active energy ray used in the present invention is light having a wavelength of 300 nm or less, laser light, electron beam, X-ray, ion beam, or plasma. By irradiating these active energy rays, hydroxyl groups or carboxyl groups can be efficiently generated on the surface of the resin plate. Moreover, as an atmosphere which irradiates these active energy rays, the state containing oxygen or ozone is preferable. A particularly simple method is a method of irradiating light from a xenon excimer lamp having a wavelength of 172 nm. When a siloxane compound is present on the surface of the resin plate, hydroxyl groups can be generated with high efficiency by irradiating light from the excimer lamp. Confirmation of the siloxane compound present on the surface of the resin plate is carried out using the X-ray photoelectron spectroscopy.
[0052]
When the resin plate exhibits elastomeric properties and can be stretched and contracted, the resin plate is stretched, irradiated with active energy rays, and further stretched, and then treated with the amino compound-containing treatment solution. By returning the resin plate to the original dimensions, amino groups can be introduced at high density.
The third method for introducing an amino group into the surface of the resin plate in the present invention is a method in which the resin plate is plasma-treated in a gas containing a nitrogen-containing compound. Nitrogen-containing compounds are nitrogen, ammonia, organic amine compounds having a vapor pressure at room temperature, and the like. The nitrogen-containing compound can be used alone, or can be used after diluted with oxygen, an inert gas, or the like. By this method, amino groups can be directly introduced into the resin plate surface at a high concentration.
[0053]
In the present invention, there are a method of using the prepared resin plate for concrete form by pasting it on the surface of the concrete form through an adhesive layer, a method of using by applying a liquid resin to the surface of the concrete form and curing it. . 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”. In particular, resin plates with low flexibility in the cured state, such as resin plates such as epoxy resins or thick resin plates, are difficult to bend and affixed to the concrete formwork. It is preferable to cure by high energy ray irradiation or heat.
[0054]
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.
[0055]
[Example 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.
[0056]
[Adjustment of photosensitive resin composition]
For 70 parts by weight of unsaturated polyurethane prepolymer a, ethylene glycol dimethacrylate 20 parts by weight, 2-aminopropyl methacrylate 10 parts by weight, photopolymerization initiator 2,2-dimethoxy-2-phenylacetophenone 0.4 parts by weight, polymerization Inhibitor 2,6-t-butyl-4-methylphenol 0.05 parts by weight was mixed to obtain photosensitive resin composition A.
[0057]
[Preparation of resin plate]
A negative film for forming a convex pattern was placed on the glass surface of Asahi Kasei Co., Ltd., flexographic plate making machine, and trademark “AWF plate making machine”, and a polyethylene terephthalate cover film having a thickness of 20 μm was placed on the negative film for vacuum contact. Next, the photosensitive resin composition A was formed on the cover film to a thickness of 2.5 mm using a carriage manufactured by Asahi Kasei Corporation. Furthermore, a base film for a photosensitive resin plate in which an adhesive having a thickness of several μm is applied on one side of a transparent polyethylene terephthalate film having a thickness of 180 μm on the photosensitive resin composition A layer is applied with an adhesive layer. Laminate so that the surface is facing down. FIG. 1A shows this state. The carriage is a traveling molding and spreading device having a laminate roller, a bucket (resin reservoir), a guide, and the like, on a spacer (a rail that moves up and down to regulate the thickness of the plate) along the glass surface. The photosensitive resin composition is cast while being run, and the photosensitive resin composition layer is spread (coated) to a predetermined thickness while feeding the base film. The negative film has a heat-sensitive material coated on one side of a 120 μm-thick transparent polyester film, and has been previously designated by the user with CAD data using a thermal head printer (trademark “thermal plotter” manufactured by Ricoh). It is a negative film of a resin plate for concrete molds produced by outputting an image in which 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 reason why the cover film is placed between the negative film and the photosensitive resin layer is to prevent the photosensitive resin from adhering to the negative film.
[0058]
Next, the photosensitive resin composition A was cured by irradiating ultraviolet rays (downward arrow in FIG. 1 (b)) from the upper part of the obtained laminate with an exposure apparatus provided in the plate making machine. FIGS. 1B and 1C show this state. After completion of the exposure, the negative film is peeled off, and the uncured portion that has not been irradiated with ultraviolet light is scraped off and collected, and then the uncured portion is completely removed with a weak alkaline detergent (trademark “W-10” manufactured by Asahi Kasei Co., Ltd.). 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 convex pattern with a height of 2.5 mm 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.
[0059]
The linear thermal expansion coefficient of the base film made of polyethylene terephthalate which is the sheet-like base material is 50 ppm / ° C. as a result of measurement using a thermomechanical measuring device (trademark “TMA-50” manufactured by Shimadzu Corporation). The melting temperature measured with a differential scanning calorimeter (trade name “DSC-50” manufactured by Shimadzu Corporation) was 245 ° C.
[0060]
The ratio of amino group-derived nitrogen atoms to carbon atoms on the surface of the obtained resin plate was determined using X-ray photoelectron spectroscopy. First, the photosensitive resin composition was cured by irradiating with ultraviolet rays to a thickness of 2.5 mm, 3 × 5 cm ² A resin plate sample was prepared. Next, 300 μl of pentafluorobenzaldehyde was dissolved in 15 ml of pentane, and the resin plate sample was reacted at 35 to 40 ° C. for 2 hours. After the resin plate sample was washed with pentane, unreacted substances were extracted with pentane for 12 hours using a Soxhlet extractor. The center part of the sample was cut out to obtain a sample for X-ray photoelectron spectroscopy. As a result of obtaining the peak intensity derived from the 1S orbital of the fluorine atom and the peak intensity derived from the 1S orbital of the carbon atom, correcting with the relative sensitivity coefficient of fluorine and carbon, and determining the ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms, It was 1 atomic%. The XPS apparatus used was a trademark “ESCA-5400” manufactured by ULVAC-PHI.
[0061]
[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.
[0062]
[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.
[0063]
"Evaluation of hardness of concrete surface"
Hardened concrete is easily released from the metal formwork, the surface of the resulting concrete is smooth and free from any deposits, and the release agent applied in the formwork is completely removed from the formwork surface. It remained attached. 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.
[0064]
In addition, it was confirmed that the time until complete curing was 10 days, which can be significantly shortened compared to 30 days of the conventional method.
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.
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 immediately after being taken out of the formwork, and the height at which the steel ball was repelled was 11 cm. .
[0065]
[Example 2]
[Prepolymer production]
A 1-L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Co., Ltd., 100 parts by weight of a trademark “PCDL L4672” (number average molecular weight 1990, OH number 56.4) and tolylene diisocyanate. After adding 6.9 parts by weight and reacting at 80 ° C. with heating for about 3 hours, adding 3.3 parts by weight of 2-methacryloyloxyisocyanate and further reacting for about 3 hours, the terminal is a methacrylic group ( A prepolymer b having a number average molecular weight of about 10,000 having an average number of polymerizable unsaturated groups in the molecule of about 2 per molecule) was produced. 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.
[0066]
[Adjustment of photosensitive resin composition]
For 70 parts by weight of the prepolymer b, benzyl methacrylate 10 parts by weight, cyclohexyl methacrylate 10 parts by weight, diethylene glycol monobutyl ether monomethacrylate 10 parts by weight, photopolymerization initiator 2,2-dimethoxy-2-phenylacetophenone 0.4 parts by weight Parts, polymerization inhibitor 2,6-t-butyl-4-methylphenol 0.05 parts by weight, and fine powder silica having an average particle size of 4.5 μm (trade name “Cyrossphere C-1504” manufactured by Fuji Silysia Chemical Ltd.) ) 5 parts by weight were mixed to obtain a photosensitive resin composition B.
[0067]
[Preparation of resin plate]
A 2.5 mm thick cured photosensitive resin composition was formed on the surface of the sheet-like substrate in the same manner as in Example 1 except that a laminate film made of a completely transparent polyester film having a thickness of 150 μm was used instead of the negative film. A sheet-like laminate in which physical layers were laminated was formed. However, since the entire surface of the photosensitive resin composition layer is exposed, it is not necessary to remove the uncured portion.
[0068]
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.
[0069]
Next, the resin plate surface on which the convex pattern was formed was treated with a silane coupling agent having an amino group to introduce amino groups on the resin plate surface. First, 5 g of γ-aminopropyltrimethoxysilane, 332 g of methanol, and 663 g of water were mixed to prepare a silane coupling agent treatment solution. Thereafter, the prepared silane coupling agent treatment liquid was uniformly and thinly applied to the surface of the resin plate, and dried at 80 ° C. for 10 minutes.
[0070]
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.
As a result of obtaining the ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms in the same manner as in Example 1, it was 1.5 atomic%.
[0071]
[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.
[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.
[0073]
"Evaluation of hardness of concrete surface"
Hardened concrete is easily released from the metal formwork, the surface of the resulting concrete is smooth and free from any deposits, and the release agent applied in the formwork is completely removed from the formwork surface. It remained attached. 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, it was confirmed that the time until complete curing was 10 days, which can be significantly shortened compared to 30 days of the conventional method.
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.
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 immediately after being taken out from the mold, and the height at which the steel ball repelled was measured to be 12 cm. .
[0075]
[Example 3]
[Preparation of resin form for concrete formwork]
A resin plate (c) for concrete formwork was prepared in the same manner as in Example 1 except that a wholly aromatic polyamide film having a thickness of 50 μm (trade name “Aramika” manufactured by Asahi Kasei Co., Ltd.) was used as the sheet-like substrate. 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 ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms was determined in the same manner as in Example 1, and the result was 1.0 atomic%.
[0076]
[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.
[0077]
[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.
[0078]
"Evaluation of hardness of concrete surface"
Hardened concrete is easily released from the metal formwork, the surface of the resulting concrete is smooth and free from any deposits, and the release agent applied in the formwork is completely removed from the formwork surface. It remained attached. 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.
[0079]
In addition, it was confirmed that the time until complete curing was 10 days, which can be significantly shortened compared to 30 days of the conventional method.
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.
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 immediately after being taken out of the formwork, and the height at which the steel ball was repelled was 11 cm. .
[0080]
[Example 4]
[Preparation of resin form for concrete formwork]
A resin plate for a concrete form having a convex pattern on the surface of the sheet-like substrate was produced in the same manner as in Example 2 except that a wholly aromatic polyamide film having a thickness of 50 μm was used as the sheet-like substrate. The surface of the resin plate was modified by treating it with a silane coupling agent having the same amino group as in Example 2. 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.
As a result of obtaining the ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms in the same manner as in Example 1, it was 1.5 atomic%.
[0081]
[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.
[0082]
[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. Further, the height of the portion having the concave pattern of the hardened concrete was lowered by the thickness of the sheet-like base material from the height defined by the dimensions of the mold.
[0083]
"Evaluation of hardness of concrete surface"
Hardened concrete is easily released from the metal formwork, the surface of the resulting concrete is smooth and free from any deposits, and the release agent applied in the formwork is completely removed from the formwork surface. It remained attached. 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.
[0084]
In addition, it was confirmed that the time until complete curing was 10 days, which can be significantly shortened compared to 30 days of the conventional method.
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.
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 immediately after being taken out of the formwork, and the height at which the steel ball was repelled was 11 cm. .
[0085]
[Example 5]
3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexyl carboxylate (Union Carbide: Trademark “UVR-6110”) 71 parts by weight, 1,9-nonanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Trademark) “Light acrylate 1,9ND-A”) 5 parts by weight, polypropylene glycol monomethacrylate (manufactured by NOF Corporation: trademark “Blenmer PP-1000”, average molecular weight 1014) 24 parts by weight, triarylsulfonium hexafluorophosphate mixture propylene Carbonate 50 wt% solution (Union Carbide: Trademark “UVI-6990”) 4 parts by weight, Trademark “BYK-UV3500” (Big Chemie Japan, Inc .: Polydimethylsiloxane having polyether-modified acrylic group) 2.0 weight Mixing parts To obtain a liquid photosensitive resin composition Te.
[0086]
The surface tension of the obtained liquid photosensitive resin composition was 42 mN / m when measured with a surface tension meter “CBVP-Z” (trademark, manufactured by Kyowa Interface Science Co., Ltd.) at 25 ° C.
The photosensitive resin composition is applied to the surface of a metal concrete mold with a thickness of about 100 μm, and then 1800 mJ / cm in air at room temperature using a 3 kW ultra-high pressure mercury lamp. ² When the ultraviolet rays were irradiated, a cured product was obtained. Next, the surface of the cured epoxy resin was irradiated with an excimer lamp having a wavelength of 172 nm in an air atmosphere to modify the surface of the epoxy resin. The excimer lamp used was a trademark “UER65783” manufactured by USHIO INC.
[0087]
Furthermore, the amino group was introduce | transduced into the epoxy resin surface by processing the said epoxy resin surface using the silane coupling agent processing liquid which has the same amino group as Example 2. FIG.
When the ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms was determined in the same manner as in Example 1, it was 2.5 atomic%.
[0088]
Next, in the same manner as in Example 1, concrete was poured into the mold and cured. Hardened concrete is easily released from the metal formwork, the resulting concrete surface is smooth and free of any deposits, and the epoxy resin layer applied in the formwork is completely on the formwork surface. It remained attached.
[0089]
Hardened concrete can be easily released from metal molds without having to apply a mold release agent to the mold surface. The resulting concrete surface is smooth, free from any deposits, The release agent applied in the frame also remained completely attached to the mold surface. 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.
[0090]
In addition, it was confirmed that the time until complete curing was 10 days, which can be significantly shortened compared to 30 days of the conventional method.
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.
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 immediately after being taken out from the mold, and the height at which the steel ball repelled was measured to be 12 cm. .
[0091]
[Example 6]
3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (manufactured by Union Carbide: trademark "UVR-6110") 51 parts by weight, trifunctional epoxy compound having a secondary hydroxyl group (manufactured by Nagase Chemical Industries) , Trademark "Deconal EX-421") 20 parts by weight, 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: trademark "Light acrylate 1,9ND-A") 5 parts by weight, two hydroxyl groups and two acrylate groups 24 parts by weight of an ethylenically unsaturated compound (manufactured by Nagase Kasei Kogyo Co., Ltd .: trademark “Deconal, DA-920”), a triarylsulfonium hexafluorophosphate mixture 50% by weight propylene carbonate solution (manufactured by Union Carbide Co., Ltd .: trademark “ UVI-6990 ") 4 parts by weight, trademark" BYK-UV35 " 0 ": was obtained (BYK Japan KK polydimethylsiloxane having polyether-modified acrylic group) 2.0 parts by weight of a mixture of liquid photosensitive resin composition.
[0092]
The photosensitive resin composition is applied to the surface of a metal concrete mold with a thickness of about 100 μm, and then 1800 mJ / cm in air at room temperature using a 3 kW ultra-high pressure mercury lamp. ² When the ultraviolet rays were irradiated, a cured product was obtained.
Furthermore, the amino group was introduce | transduced into the epoxy resin surface by processing the said epoxy resin surface using the silane coupling agent processing liquid which has the same amino group as Example 2. FIG.
When the ratio of the number of nitrogen atoms derived from an amino group to the number of carbon atoms was determined in the same manner as in Example 1, it was 2.0 atomic%.
Next, in the same manner as in Example 1, concrete was poured into the mold and cured. Hardened concrete is easily released from the metal formwork, the resulting concrete surface is smooth and free of any deposits, and the epoxy resin layer applied in the formwork is completely on the formwork surface. It remained attached.
[0093]
Hardened concrete can be easily released from metal molds without having to apply a mold release agent to the mold surface. The resulting concrete surface is smooth, free from any deposits, The release agent applied in the frame also remained completely attached to the mold surface. 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.
[0094]
Furthermore, it was found that rust does not occur on the surface of the formwork and has a rust prevention effect.
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 immediately after taking out from the mold, and the height at which the steel ball repels was measured. there were.
[0095]
[Example 7]
By applying and heating an epoxy adhesive with a thickness of 20 μm on a 50 μm thick wholly aromatic polyamide film (trade name “Aramika” manufactured by Asahi Kasei Co., Ltd.) having fine irregularities formed by wet blasting on the surface. Semi-cured state. Further, a laminated body bonded by hot pressing silicon rubber having a thickness of 2.5 mm on the adhesive layer was obtained.
[0096]
Next, in the same manner as in Example 2, the silicon rubber layer was engraved with a carbon dioxide laser until the epoxy resin layer was exposed to obtain a resin plate having a convex pattern formed on the aramid film.
The surface of the obtained resin plate was irradiated with excimer lamp light having a wavelength of 172 nm in an air atmosphere to generate hydroxyl groups on the surface of the resin plate.
By treating the obtained resin plate surface with the same silane coupling agent treatment solution having an amino group as in Example 2, amino groups were introduced onto the resin plate surface.
[0097]
When the ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms was determined in the same manner as in Example 1, it was 2.5 atomic%.
Next, in the same manner as in Example 1, concrete was poured into the mold and cured. Hardened concrete is easily released from the metal formwork, the resulting concrete surface is smooth and free of any deposits, and the epoxy resin layer applied in the formwork is completely on the formwork surface. It remained attached.
[0098]
Hardened concrete can be easily released from metal molds without having to apply a mold release agent to the mold surface. The resulting concrete surface is smooth, free from any deposits, The release agent applied in the frame also remained completely attached to the mold surface. The concave pattern corresponding to the convex pattern on the surface of the resin plate could be faithfully transferred to the concrete surface.
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.
[0099]
Furthermore, it was found that rust does not occur on the surface of the formwork and has a rust prevention effect.
Further, 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 11 cm.
[0100]
[Example 8]
A silicon rubber plate with a thickness of 0.5 mm is attached to the mold, and a hydroxyl group is generated on the surface of the silicon rubber plate by irradiating light from an excimer lamp with a wavelength of 172 nm in an air atmosphere with the four sides extended by 10%. I let you.
Next, in the stretched state, the silicon rubber was treated with the same silane coupling agent having an amino group as that used in Example 2, and after the amino group was introduced to the rubber plate surface, it was removed from the mold, Returned to dimensions.
[0101]
When the ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms was determined in the same manner as in Example 1, it was 3.0 atomic%.
The silicon rubber plate was bonded to the concrete mold with an adhesive so that the surface treated was exposed.
Next, in the same manner as in Example 1, concrete was poured into the mold and cured. Hardened concrete is easily released from the metal formwork, the resulting concrete surface is smooth and free of any deposits, and the epoxy resin layer applied in the formwork is completely on the formwork surface. It remained attached.
[0102]
Hardened concrete can be easily released from metal molds without having to apply a mold release agent to the mold surface. The resulting concrete surface is smooth, free from any deposits, The release agent applied in the frame also remained completely attached to the mold surface. 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 place on the concrete surface was struck five times by dropping the hammer from its height of about 30 cm with its own weight without applying force.
[0103]
Furthermore, it was found that rust does not occur on the surface of the formwork and has a rust prevention effect.
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 immediately after being taken out from the mold, and the height at which the steel ball repelled was measured to be 12 cm. .
[0104]
[Example 9]
By exposing the surface of a polyethylene film having a thickness of 200 μm to a plasma of nitrogen gas containing 10% by volume of ammonia gas, amino groups were introduced on the surface of the polyethylene film. The plasma processing apparatus used was a trade mark “Plasma Asher PC1000-5030” manufactured by Yamato Scientific Co., Ltd. The temperature of the sample stage on which the sample is placed can be controlled, and the sample is cooled during plasma processing so that the temperature of the sample does not increase.
[0105]
When the ratio of the number of nitrogen atoms derived from the amino group to the number of carbon atoms was determined in the same manner as in Example 1, it was 1.5 atomic%.
The silicon rubber plate was bonded to the concrete mold with an adhesive so that the surface treated was exposed.
Next, in the same manner as in Example 1, concrete was poured into the mold and cured. Hardened concrete is easily released from the metal formwork, the resulting concrete surface is smooth and free of any deposits, and the epoxy resin layer applied in the formwork is completely on the formwork surface. It remained attached.
[0106]
Hardened concrete can be easily released from metal molds without having to apply a mold release agent to the mold surface. The resulting concrete surface is smooth, free from any deposits, The release agent applied in the frame also remained completely attached to the mold surface. 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 place on the concrete surface was struck five times by dropping the hammer from its height of about 30 cm with its own weight without applying force.
[0107]
Furthermore, it was found that rust does not occur on the surface of the formwork and has a rust prevention effect.
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 immediately after being taken out of the formwork, and the height at which the steel ball was repelled was 11 cm. .
[0108]
[Comparative Example 1]
A concrete mold resin plate (v) having a convex pattern on the surface was prepared in the same manner as in Example 2 except that the surface of the resin plate was not treated with a silane coupling agent having an amino group. There are no amino groups on the surface of the resin plate.
[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.
[0109]
[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.
[0110]
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 almost completely transferred was obtained. There was a part where the concrete bite into the resin plate surface in a part of the minute pattern part.
[0111]
In the second concrete placement, a release agent made of mineral oil was sprayed on the surface of the resin plate so that the hardened concrete can be easily taken out from the mold, and the concrete was poured into the mold by the above method and cured. . Hardened concrete became easier to remove from the formwork.
On the surface of the concrete taken out from the mold for the second time, mineral oil as a release agent was transferred, and color unevenness was present on the surface. Further, it took 30 days to completely harden the concrete taken out from the mold. Furthermore, when the hardness of the concrete surface immediately after taking out from a formwork was evaluated by the method of dropping a steel ball in the same manner as in Example 1, the height of repulsion was 7 cm.
[0112]
[Comparative Example 2]
In the same manner as in Example 2, the surface of a natural rubber plate having a thickness of 3 mm was irradiated with a carbon dioxide laser beam to engrave an uneven pattern having a depth of 1.5 mm, thereby producing a rubber plate for concrete formwork. Next, the rubber plate obtained in the same manner as in Example 1 was attached to a concrete formwork with the surface where the pattern was present facing up. No amino group was present on the surface of the rubber plate.
[0113]
Thereafter, in the same manner as in Example 1, concrete was poured into the mold and cured. When removing the hardened concrete from the formwork, it was difficult to remove the concrete, and some pieces of concrete dig into the rubber plate. Therefore, the surface of the produced concrete was not a complete transfer of the rubber plate pattern.
[0114]
【The invention's effect】
According to the present invention, it is excellent in releasability, there is no chipping of the formed concrete at the time of demolding, and an uneven pattern is formed by faithfully copying the pattern of the resin plate on the surface of the obtained concrete. Resin plate for concrete formwork that has excellent durability that can be used repeatedly, has no traces of bubbles, no traces of bubbles, and has a hardened concrete surface that can be cured completely after being removed from the formwork. Can be provided.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an explanatory view showing a process for producing a resin plate of an embodiment of the present invention, wherein (a) to (d) show the process order.
[Explanation of symbols]
1 Base film
2 Photosensitive resin layer
3 Negative film
4 Cured photosensitive resin
5 Cover film

Claims (9)

A resin plate mounted on the surface of a concrete formwork, where an amino group having active hydrogen is present on the surface, and the surface amino group when measured using X-ray photoelectron spectroscopy (XPS method) The ratio of the number of nitrogen atoms to the number of carbon atoms is from 0.1 atomic% to 20 atomic%, and the resin plate for concrete formwork. The resin plate for a concrete mold according to claim 1, wherein the resin plate has a convex pattern prepared by irradiating the photosensitive resin composition with high energy rays. The photosensitive resin composition is essential for (A) a prepolymer having a number average molecular weight of 1,000 to 500,000, (B) a reactive monomer having a polymerizable reactive group having a molecular weight of less than 1000, and (C) a photopolymerization initiator. As a component, the component (A) or (B) contains 1 to 70 wt% of the total weight of (A) and / or (B) the compound (D) in which an amino group having active hydrogen is present in the molecule, (A) 5 to 200 parts by weight of component (B) with respect to 100 parts by weight, and 0.1 to 10% by weight of component (C) with respect to the total weight of components (A) and (B) The resin plate for concrete mold according to claim 2, wherein: The component (A) of the photosensitive resin composition is an unsaturated polyurethane prepolymer having a plurality of diol segments bonded via urethane bonds, and having an ethylenically unsaturated group at at least one end, and the component (B) is The resin plate for a concrete mold according to claim 3, wherein the resin plate is a reactive monomer having at least one ethylenically unsaturated bond. The resin plate for a concrete mold according to claim 1, further comprising a filler having a hydroxyl group on the surface having a number average particle diameter of 0.01 µm to 100 µm. Non-photosensitive resin composition containing 5-50 wt% of polymer containing 1-50% of monomer units having amino groups as raw material for resin plate, or prepolymer and / or reactive monomer component The method for producing a resin plate according to claim 1, wherein a photosensitive resin composition containing 1 to 70 wt% of a polymerizable reactive compound having an amino group therein is used. 2. The method for producing a resin plate for a concrete mold according to claim 1, comprising a step of treating the resin plate surface with a treatment liquid containing a compound containing an amino group and fixing the amino compound to the resin plate surface. . The resin plate for a concrete mold according to claim 1, wherein the resin plate has a convex pattern on the surface, and the method of forming the convex pattern is a method of removing the resin by irradiating a laser. Forming method. 2. The method for forming a resin plate for a concrete mold according to claim 1, wherein the surface of the resin plate is subjected to plasma treatment in a gas containing a nitrogen-containing compound.

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