JP2003266416A - Resin plate for concrete form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin plate for a concrete form which has a high dimensional stability, which is a resin plate having a high thickness accuracy and which can extremely approach a height of a cured concrete to a designed value. <P>SOLUTION: The resin plate for the concrete form has a protruding pattern on a surface used by adhering to a surface of the form. The resin plate comprises the protruding pattern having a height of 0.01 to 50 mm and made of a photosensitive resin composition on one side surface of a sheet-like base having a thickness of 0.01 to 1 mm, so that a linear thermal expansion coefficient of the base is 100 ppm/&deg;C or less. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin plate for imparting an uneven pattern to the surface of concrete, which is excellent in dimensional stability, and is excellent in mold releasability from hardened concrete.
The present invention relates to a resin plate for concrete formwork capable of improving the hardenability of the surface of concrete.

[0002]

2. Description of the Related Art In recent years, various methods have been proposed for producing concrete in which an uneven pattern is provided on the surface of the concrete to improve its design. For example, a method of engraving a rubber plate with a knife to give an uneven pattern to the surface, preparing a metal or plastic mold with a pattern, and stacking the mold and the rubber plate and then hot pressing the mold. Or a method for producing a resin plate having an uneven pattern by using a photoengraving technique is disclosed in JP-A-1-171807 and JP-A-3-63354. .

In the conventional method, since a rubber layer or a resin layer having a thickness of up to several mm is present at the bottom of the recess in the uneven pattern formed on the surface of the rubber plate or the resin plate, the surface of these plates may be affected. When the pattern formed on the plate was transferred to concrete, the thickness of the concrete was reduced by the thickness of the rubber layer or resin layer remaining at the bottom of the recess of the plate. For example, in the case of a concrete secondary product whose standard is fixed, such as a U-shaped groove lid, there is a problem that it is necessary to correct the dimensions of the concrete formwork for the reduced thickness. It was Therefore,
It was necessary to make the thickness W of the rubber layer or resin layer remaining at the bottom of the recess of the plate shown in (4) as thin as possible, but when trying to make it thin, the through holes were partially opened, and in some cases the pattern was cut off. There was a problem in plate making such as being lost. Further, JP-A-1-171807 describes a method for producing a resin plate having an uneven pattern by using a photosensitive resin and a photoengraving technique. in this way,
Form a photosensitive resin layer on a sheet-shaped base material, first irradiate the entire surface of the photosensitive resin layer with light from the sheet-shaped base material side to form a thick base part, and then from the other side surface to a negative film It is a method of irradiating light passing through the composition to cure the photosensitive resin, and forming an uneven pattern through a developing process. Therefore,
Since the thick resin layer exists at the bottom of the recess, it does not solve the problem of the resin remaining at the bottom of the recess, which has been a problem in conventional rubber plates and the like.

In any of the methods, a rubber plate or resin plate having an uneven pattern is fixed to a concrete mold made of metal such as iron or aluminum, wood such as natural wood or plywood, or plastic using an adhesive or the like. Then, before pouring concrete into the formwork, mineral oil, heavy oil, paraffin, grease, vaseline, on the surface of the rubber plate or resin plate,
By applying a release agent whose main component is soapy water,
After the concrete hardens, it is easy to remove from the formwork. Further, since the releasing agent does not have a sustained releasing effect, it is applied each time before the concrete is poured. Further, since the mold release agent that is generally used inhibits the hardening reaction of the concrete surface, the hardening of the surface is slow, and it takes a long time to completely harden it, and in a typical example, it takes about one month. However, the concrete product produced during this period needs to be stored as it is, which leaves a big problem that productivity is extremely low.

When curing concrete, 60
From 80 to 80 ° C for several hours, in order to make contact with the strong alkaline raw cocolate,
Conventional rubber plates and resin plates still have problems in terms of dimensional stability. Further, since bubbles and bubble marks are generated on the formed concrete surface, it is difficult to faithfully transfer the uneven pattern on the resin plate surface. Further, since the surface is contaminated with a release agent in a stain-like manner, the aesthetic appearance is deteriorated by discoloration, and when aesthetic appearance is required, a step of repairing the entire surface is required, which leaves a problem. Further, from the viewpoint of designability, the uneven pattern formed on the concrete surface is a mixture of patterns of extremely various sizes. Therefore, a resin plate capable of forming a pattern with a fine dimension as designed is desired, and from this viewpoint, a photosensitive resin material capable of forming a cured product having high resolution and high durability is required. It was

[0006]

[Problems to be Solved by the Invention] The dimensional accuracy is high, the mold releasability is excellent, the concavo-convex pattern faithfully copying the pattern of the resin plate can be formed on the surface of the concrete, and the durability is excellent that it can be repeatedly used. A resin plate for concrete formwork and a method for forming the same.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a photosensitive resin layer formed on the surface of a thin sheet-like base material having high dimensional stability is irradiated with high energy rays. A resin plate having a convex pattern formed on the surface of the sheet-shaped substrate by curing and removing the uncured portion not irradiated with the high energy rays, or a sheet-shaped substrate having high dimensional stability By using the plate on which the rubber layer or resin layer formed on the surface of the is engraved with a laser to form a convex pattern on the surface, the concave pattern corresponding to the convex pattern on the surface of the resin plate can be faithfully reproduced on the surface of the hardened concrete. , And by using a thin sheet-shaped substrate, it is possible to suppress a decrease in the thickness of concrete to a low level. Furthermore, they have found that the concrete hardened by heating and curing can be easily taken out from the mold, and that a surprising effect that cannot be expected with conventional resin plates is exhibited, and the present invention has been completed. That is, the present invention provides the following resin plates for concrete formwork in order to solve the above problems. The resin plate of the present invention,
Secondary concrete products manufactured in-plant such as road concrete products, river maintenance concrete products, slope concrete products, residential land development concrete products, etc. by pasting on the surface of metal, wooden or plastic formwork. ,
Alternatively, it is used for a concrete structure constructed by a cast-in-place concrete method.

The first aspect of the present invention is a resin plate comprising a sheet-shaped base material and a photosensitive resin cured product layer having a convex pattern, which is used by mounting it on the surface of a concrete formwork. Has a thickness of 0.01 mm or more and 1 mm or less, and the convex pattern of the photosensitive resin cured product has a height of 0.01 mm or more and 50 m
A resin plate for a concrete formwork having a thickness of m or less and a resin residual layer in a portion where the convex pattern does not exist is 10% or less of the convex pattern; the second of the present invention has a melting temperature of 150. The resin plate for a concrete formwork according to claim 1, which has a temperature of not less than 0 ° C; the third aspect of the present invention is that the cured product of the photosensitive resin comprises (A) a plurality of diol segments bonded via urethane bonds, An unsaturated polyurethane prepolymer having an ethylenically unsaturated group at one end, (B) a reactive monomer having at least one or more ethylenically unsaturated bonds, and (C) a resin composition containing a photopolymerization initiator The resin plate for concrete formwork according to claim 2, which is a cured product.

A fourth aspect of the present invention is the resin plate for concrete formwork according to claim 1, wherein the cured photosensitive resin material contains a filler having a number average particle diameter of 0.1 μm or more and 100 μm or less. Yes; in the fifth aspect of the present invention, a thickness of 0.001 μm or more between the sheet-shaped base material and the photosensitive resin cured product layer
The resin plate for concrete formwork according to claim 1, wherein an adhesive layer having a thickness of 0 μm or less is present; a sixth aspect of the present invention is the surface of a sheet-shaped substrate having a thickness of 0.01 mm or more and 1 mm or less. Is provided with a photosensitive resin composition layer, and a negative film for providing a convex pattern is further spread thereon, and the composition is irradiated with high energy rays to cure the composition, and the composition is not exposed to high energy rays. By removing the uncured portion, a height of 0.01 mm or more on the sheet-shaped substrate 50
to form a convex pattern of a cured photosensitive resin of less than mm,
A method for producing a resin plate for concrete formwork, characterized in that the thickness of the resin residual layer having no convex pattern is 10% or less of the convex pattern;

A seventh aspect of the present invention is the method according to claim 6, wherein the surface of the cured photosensitive resin on the side where the convex pattern is present is treated with a treatment liquid containing a coupling agent. Yes; the eighth aspect of the present invention is a thickness of 0.01 mm or more 1
A liquid photosensitive resin composition layer is provided on the surface of a sheet-shaped substrate having a size of not more than mm, and the entire surface of the liquid photosensitive resin layer is irradiated with a high energy ray to cure the photosensitive resin layer and further irradiate a laser. By removing the photosensitive resin cured product layer by this, a convex pattern of the photosensitive resin cured product having a height of 0.01 mm or more and 50 mm or less is formed on the sheet-shaped substrate, and the convex pattern does not exist. A method for producing a resin plate for concrete formwork, characterized in that the thickness of the resin residual layer is 10% or less of the convex pattern; and the ninth aspect of the present invention is the ninth aspect of the present invention. This is a concrete formwork obtained by mounting the resin plate of (1) on the surface of the concrete formwork via an adhesive layer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The linear thermal expansion coefficient of the sheet-shaped substrate used in the present invention is 100 ppm / ° C. or less, preferably 80 ppm /
℃ or less, more preferably 70ppm / ℃ or less. If the coefficient of linear thermal expansion exceeds 100 ppm / ° C and is large, the resin plate attached to the surface of the concrete form may warp or peel off during the curing process of the concrete at high temperature.
It becomes difficult to faithfully transfer the pattern on the resin plate surface. In the present invention, the coefficient of linear thermal expansion is measured using a thermomechanical measurement method.

The melting temperature of the sheet-shaped substrate used in the present invention is preferably 150 ° C. or higher, more preferably 20.
The temperature is 0 ° C or higher, more preferably 220 ° C or higher. The melting temperature is a temperature at which the resin fluidizes, and is measured by a differential scanning calorimetry method in the present invention, 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-shaped substrate is likely to be deformed in a temperature environment of 60 ° C to 80 ° C used for hardening concrete.

The thickness of the sheet-like substrate used in the present invention is
0.01 mm or more and 1 mm or less, preferably 0.03 mm
It is 0.05 mm or less and more preferably 0.05 mm or more and 0.02 mm or less. If the thickness is less than 0.01 mm, there is a problem that wrinkles may be formed or cut when handling the sheet-shaped substrate, and if it exceeds 1 mm, the thickness of the hardened concrete may be thin. As the material of the sheet-shaped 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 polyether sulfone resin, liquid crystal resin made of wholly aromatic polyester resin, wholly aromatic polyamide resin, and epoxy resin. Further, these resins may be laminated and used. For example, it is a sheet in which a 50 μm-thick polyethylene terephthalate layer is laminated on both sides of a 4.5 μm-thick wholly aromatic polyamide film.

Further, as a method for reducing the linear thermal expansion coefficient of the sheet-shaped substrate, a method of adding a filler, a method of impregnating or coating a resin on a mesh-like cloth such as wholly aromatic polyamide or glass cloth, etc. Can be mentioned. As the filler, commonly used organic fine particles, inorganic fine particles of metal oxides or metals, organic / inorganic composite fine particles, and the like can be used. It is also possible to use porous fine particles, fine particles having cavities inside, microcapsule particles, and layered compound particles in which a low molecular weight compound is intercalated. Especially alumina,
Metal oxide fine particles such as silica, titanium oxide and zeolite, latex fine particles made of polystyrene / polybutadiene copolymer, organic fine particles of natural products such as cellulose are useful.

By physically or chemically treating the surface of the sheet-shaped 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 of ejecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or a vacuum ultraviolet ray irradiation method. The chemical treatment method includes a strong acid / strong alkali treatment method, an oxidizing agent treatment method, a coupling agent treatment method and the like.

The method for forming the resin-made convex pattern on the surface of the sheet-shaped substrate is as follows: a photosensitive resin which is cured by irradiation with high energy rays is processed by photolithography, and a laser is irradiated. And a method of removing the resin by melting or ablation. In the convex pattern formed on the surface of the sheet-shaped substrate, the height of the convex portion is 0.01 mm.
50 mm or less, preferably 0.1 mm or more and 50 mm
Hereafter, it is more preferably 0.5 mm or more and 30 mm or less. If the height is less than 0.01 mm, it is not sufficient for imparting a design property to the concrete surface, and if it exceeds 50 mm, it becomes difficult to remove the hardened concrete from the mold.

Further, on the surface of the sheet-shaped substrate on which the convex pattern is formed, the thickness of the resin layer remaining on the surface of the portion where the convex pattern does not exist is preferably as thin as possible. The thickness of the resin residual layer is 10% or less, preferably 5% or less, and more preferably 1% or less of the height of the convex pattern. If the thickness of the resin residual layer is larger than 10% of the height of the convex pattern, the thickness of the hardened concrete becomes thin, and the depth of the concave pattern transferred to the concrete becomes small, which may decrease the design dimension. It will be out of the standard. The thickness of the resin residual layer and the height of the convex pattern strongly depend on the energy amount of the high-energy rays with which the photosensitive resin composition is irradiated and the parallelism of rays of the high-energy rays. When the amount of energy of the high-energy rays to be irradiated is excessively large, the reflected light from the base material causes curing in the vicinity of the base material side of the portion that is not originally cured due to the light-shielding portion of the negative film, and is not removed in the developing process. Will remain. Further, when the parallelism of the high-energy rays is low and the rays spread, the leakage of the rays to the light-shielding portion of the negative film becomes large, and the thickness of the resin residual layer also becomes large.
However, if you increase the parallelism of the rays and bring them closer to parallel rays,
It becomes difficult to form a tapered shape on the convex pattern. Therefore, it is necessary to adjust the optical system such as the distance from the negative film to the light source. Further, in the negative film, the finer the light-shielding portion, the more the thickness of the resin residual layer tends to increase. Therefore, it is necessary to adjust the size of the light-shielding portion of the negative film, the amount of energy of the high-energy rays, and the parallelism of rays of the high-energy rays to keep the thickness of the resin residual layer low. Further, the thickness of the resin residual layer is significantly dependent on the curing performance of the photosensitive resin composition used,
It is desirable to select a photosensitive resin composition having a high resolution. On the other hand, in the method of irradiating a laser beam to remove 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. . In this method, the beam diameter of the laser light can be narrowed down to 50 μm or less,
It has a feature that the size of a pattern that can be processed can be set to be about the beam diameter of laser light.

Further, in the present invention, the convex pattern formed on the surface of the sheet-shaped substrate has a taper toward the sheet-shaped substrate. That is, as shown in FIG. 3, the taper angle R from the top direction of the convex pattern toward the sheet-shaped substrate is 5
It is preferably 0 ° or more and 85 °. The taper angle is preferably 50 ° or more from the viewpoint of forming a pattern of a predetermined height with high density, and is preferably 85 ° or less from the viewpoint of releasability of the hardened concrete. In photolithography, a high-energy ray from a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, etc. is applied to the photosensitive resin composition layer, and the exposed portion is cured to remove the uncured portion. Go through the developing process. In the development process, the uncured resin is physically scraped off using a spatula, the treatment liquid that can be dissolved or dispersed is sprayed or immersed in the treatment liquid, and uncured by irradiation with high-pressure / high-temperature steam. It is possible to use a method of melting and removing the part, or a method of applying heat to the resin plate to melt the uncured part with a sponge-like sheet and adsorbing and removing it.

In the method of irradiating the resin with a laser beam to ablate and melt the resin, an uneven pattern can be directly formed without a developing step. The laser used includes a carbon dioxide gas laser, a YAG laser having an oscillation wavelength in the infrared region, a third YAG laser,
A typical laser that can be used is one that has an oscillation wavelength in the ultraviolet region such as a fourth harmonic wave or an excimer laser.
Next, the photosensitive resin composition which can be used in the resin plate application for concrete formwork of the present invention and which can form a cured product having high resolution and high durability will be described.

The component (A) constituting the photosensitive resin composition according to claim 2 of the present invention is preferably a prepolymer having a number average molecular weight of 1,000 or more and 500,000 or less. As the condensation type polymer, polyurethane resin, polyester resin, unsaturated polyester resin, polyimide resin, polysulfone resin, polyamide resin, polycarbonate resin or the like, and as the addition polymerization type polymer, polystyrene resin, polyethylene resin, polypropylene resin or other polyolefins , A homopolymer or a copolymer such as a polybutadiene resin, and a ring-opening polymer as an epoxy resin,
Examples thereof include polysiloxanes. With a prepolymer having a number average molecular weight of less than 1000, it is difficult to secure the mechanical properties and flexibility of the cured product formed by irradiation with high energy rays, and when it exceeds 500,000, the viscosity of the photosensitive resin composition is high. Is significantly increased, and it becomes difficult to dissolve or disperse the uncured product in a developing solution when removing the uncured product in the developing step.
Preferably 2000 or more and 100,000 or less, more preferably 2
It is 000 or more and 25,000 or less. The number average molecular weight of the present invention is determined by gel permeation chromatography (GP
It is measured by the method C) and has a very narrow molecular weight distribution and is obtained by conversion with polystyrene having a known molecular weight.

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 is reacted with a diisocyanate compound to obtain a polyurethane, and then the polyurethane is reacted with a hydroxyl group- or amino group-containing ethylenically unsaturated compound or an isocyanate group-containing ethylenically unsaturated compound.

As the diol compound for obtaining the above polyurethane, a compound having two hydroxyl groups in one molecule,
For example polypropylene glycol adipate diol,
Examples include polyester diols such as polyneopentyl glycol adipate diol, polybutylene glycol adipate diol, polycaprolactone diol, and polyvalerolactone diol, and polyether diols such as polyethylene glycol diol, polypropylene glycol, polytetramethylene glycol, and polycarbonate diol. Can be mentioned.

The molecular weight obtained from the hydroxyl value of the diol compound is usually about 400 to 5,000.
5 from the perspective of obtaining a softer and stronger polyurethane
It is preferable to use one having a molecular weight of about 00 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. Among these, tolylene diisocyanate is preferred because it does not increase the viscosity of the polyurethane obtained so much and is flexible and easy to obtain.

Examples of the hydroxyl group-containing ethylenically unsaturated compound which is reacted with the polyurethane include hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, N-methylol acrylamide, polyoxyethylene glycol monomethacrylate, polyoxypropylene glycol. Monomethacrylate etc. can be mentioned as an example. Of these, hydroxyethyl methacrylate and hydroxypropyl methacrylate are preferable from the viewpoint of flexibility and strength, and hydroxypropyl methacrylate, which has excellent water resistance, is most preferable.

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.

When a hydroxyl group-containing ethylenically unsaturated compound is used in the preparation of unsaturated polyurethane, first, a polyurethane having isocyanate groups at both ends is synthesized by reacting the above-mentioned diol compound and a diisocyanate compound, and a hydroxyl group-containing ethylenically unsaturated compound is added thereto. React. in this case,
In order to suppress the side reaction and complete the reaction in a short time, a hydroxyl group-containing ethylenically unsaturated compound is usually added in excess of about 2 to 5 times equivalent to the polyurethane having isocyanate groups at both ends to contain an ethylenically unsaturated bond. It is preferred to obtain a mixture of polyurethane and an excess of hydroxyl-containing ethylenically unsaturated compounds.

On the other hand, when an isocyanate group-containing ethylenically unsaturated compound is used for the preparation of unsaturated polyurethane, first, a polyurethane having hydroxyl groups at both ends is synthesized by reacting the above-mentioned diol compound with a diisocyanate compound, and then the isocyanate group-containing ethylenically unsaturated compound is prepared. React the compound. In this case, the isocyanate group-containing ethylenically unsaturated compound, the number of the isocyanate group is generally added in the same range as the number of hydroxyl groups of the hydroxyl group at both ends or a small number, but facilitates stirring. In order to suppress side reactions, it is preferable to add a component that does not participate in the urethanization reaction as a diluent to reduce the viscosity of the reaction system. When the isocyanate group-containing ethylenically unsaturated compound is excessively added to the polyurethane having hydroxyl groups at both ends, it is preferable to eliminate the excess isocyanate group by adding a compound having active hydrogen such as a hydroxyl group after completion of the reaction.

Further, a polar group such as a carboxyl group can be introduced into the unsaturated polyurethane. The introduction of a carboxyl group into an unsaturated polyurethane is carried out, for example, by adding an ethylenically unsaturated compound containing 2 hydroxyl groups to a polyurethane having isocyanate groups at both ends, and reacting 1 hydroxyl group with an isocyanate group to obtain 2 hydroxyl groups. And an unsaturated polyurethane having two ethylenically unsaturated bonds,
Further, an acid anhydride is added to cause a ring-opening reaction with the hydroxyl group of the polyurethane, whereby an unsaturated polyurethane having both a carboxyl group and an ethylenically unsaturated bond at both ends can be obtained.

Examples of the ethylenically unsaturated compound containing two hydroxyl groups used herein include hydroxyl groups bonded to primary and secondary carbons such as compounds obtained by adding water to glycidyl methacrylate or acrylate to open the epoxy group. The one with 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 an isocyanate group can be obtained.

Acid anhydrides used for introducing a carboxyl group by ring-opening reaction with a hydroxyl group include succinic acid,
Examples thereof include phthalic anhydride and maleic anhydride. An unsaturated polyester may be used as an additive component instead of the unsaturated polyurethane. 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 end hydroxyl groups or both end carboxyl group polyesters are synthesized by a 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 end functional groups is reacted. You can also get it.

As the diol compound, ethylene glycol, diethylene glycol, polyethylene glycol,
Propylene glycol, polypropylene glycol, butanediol and the like can be mentioned as examples. Examples of the dicarboxylic acid compound include adipic acid, azelaic acid, sebacic acid, isophthalic acid, succinic acid, phthalic anhydride, saturated dicarboxylic acids such as terephthalic acid, fumaric acid, maleic acid, and ethylenically unsaturated dicarboxylic acids such as maleic anhydride. It can be illustrated.

As the reactive monomer having a polymerizable reactive group according to claim 2 of the present invention, a vinyl group, an acrylic group,
Monomers having ethylenically unsaturated groups such as methacrylic groups, or cyclic ethers such as epoxies and oxetanes,
Examples thereof include monomers having a ring-opening polymerizable reactive group such as cyclic carbonate, lactone, lactam and cyclic acetal. The monomer may contain a monofunctional monomer having one polymerizable reactive group, but it is preferable that the polyfunctional monomer having two or more is contained in an amount of 10 wt% or more, preferably 20 wt% or more based on the total weight of the monomers. However,
If the content of the polyfunctional monomer having 3 or more polymerizable reactive groups is 50 wt% or more based on the total weight of the monomers, the viscosity of the photosensitive resin composition is significantly increased and the subsequent processability is deteriorated, which is not preferable. Further, a compound having an ethylenically unsaturated group and a ring-opening polymerizable reactive group in the molecule at the same time may be used. Further, a monomer having an ethylenically unsaturated group and a monomer having a ring-opening polymerizable reactive group can be mixed and used.

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,
Monofunctional monomers such as dicyclopentenyloxyethyl (meth) acrylate, lauryl (meth) acrylate polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and methyltriethylene glycol (meth) acrylate,
Ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl 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 ,
Bifunctional monomers such as propylene oxide-modified bisphenol A di (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate,
Caprolactone modified tri (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( It is possible to increase polyfunctional monomers such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

As the monomer having a ring-opening polymerizable reactive group, an epoxy compound, an oxetane compound, a cyclic ester compound, a dioxolane compound, a spiro orthocarbonate compound, a spiro orthoester compound, a bicycloorthoester compound, a cyclosiloxane compound, a cyclic imino. Examples thereof include ether compounds, cyclic imine compounds, bicyclic urea compounds, cyclic carbonate compounds, cyclic sulfite compounds, and lactam compounds. 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.

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 and an epoxycyclohexyl group in the molecule. Specific examples include 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 of ethylene oxide or propylene oxide is added to bisphenol A,
Polytetramethylene glycol diglycidyl ether,
Examples thereof include poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, and poly (caprolactone) diol diglycidyl ether.
As another example, a polyepoxy compound obtained by reacting a compound having two or more olefins in the molecule with a peracid such as peracetic acid, that is, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexyl Carboxylate, 1-methyl-3,4-epoxycyclohexylmethyl-1′-methyl-3 ′, 4′-epoxycyclohexylcarboxylate, bis [1-adipate
Methyl-3,4-epoxycyclohexyl] ester,
Examples thereof include vinylcyclohexene diepoxide, polyepoxy compounds obtained by reacting polydienes such as polybutadiene and polyisoprene with peracetic acid, and epoxidized soybean oil.

As the oxetane compound used in the present invention, a commonly used compound can be used, and it is not particularly limited, but xylylene dioxetane (trade name "OXT-" manufactured by Toagosei Co., Ltd. 12
1 "), 3-ethyl-3-hydroxymethyloxetane (trade name" OXT-101 "manufactured by Toagosei Co., Ltd.), trade names" OXT-221 "and" PNOX-100 manufactured by Toagosei Co., Ltd. "
9 ”and the like. In addition, examples of the cyclic ester compound include compounds having an ε-caprolactone ring, a γ-butyrolactone ring, and a β-propionlactone ring. Further, compounds having different ring-opening polymerizable reactive groups in one molecule may be used.

Examples of the photopolymerization initiator according to the second aspect of the present invention include photoradical generators and photoacid generators. As the photo-radical generator, a commonly used one can be used. As a specific example, 4-
Phenoxydichloroacetophenone, 2-t-butyltrichloroacetophenone, diethoxyacetophenone,
1-phenyl-2-hydroxy-2-methylpropane-
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-methylpropan-1-one, 1-
Hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl 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, - diethyl thioxanthone,
2,4-isopropylthioxanthone, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxy ester, 9,10-phenanthrenequinone, camphorquinone, benzyl, 3,3 ′, 4.
4'-tetra (t-butylperoxycarbonyl) benzophenone, dibenzosuberone, 2-ethylanthraquinone, triethanolamine, methyldiethanolamine, triisopropanolamine, Michler's ketone,
4,4′-diethylaminophenone, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-
Butoxy) ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid and the like.

Specific examples of the photoacid generator include triarylsulfonium salts having BF ₄ —, PF ₆ —, SbF ₆ —, etc. as counter ions, diaryl iodonium salts, aryl diazonium salts, and the like. Commercially available photocationic polymerization initiators such as reel sulfonium hexafluorophosphate and p-thiophenoxyphenylsulfonium hexafluorophosphate can be used. These have a function of generating an acid such as Lewis acid or Bronsted acid upon irradiation with high energy rays to cause a curing reaction. From the viewpoint of curability, triarylsulfonium salts are preferable. Among them, triarylsulfonium hexafluorophosphate is excellent in thick film curability.

The photopolymerization initiator used in the present invention is preferably 0.1 to 10 wt% with respect to the total weight of the prepolymer component (A) and the reactive monomer component (B). 0.1 wt
If it is less than%, the concentration of radical species or acid generated by absorbing actinic radiation tends to be low, and the curing reaction is difficult to proceed sufficiently. If it exceeds 10 wt%, a large amount of reaction products that absorb high energy rays and generate radical species or acids tend to remain in the cured product, tending to deteriorate the mechanical properties of the cured product.

In the present invention, the resin plate may contain a filler having a number average particle diameter of 0.1 μm or more and 100 μm or less. More preferably, the number average particle diameter is 0.1 μm.
The particles are 10 μm or less. The number average particle size is 0.
If it is less than 1 μm, the viscosity of the photosensitive resin composition increases, and it tends to be difficult to defoam. Also, 100μ
When it is larger than m, it tends to be difficult to form a fine pattern.

Specifically, as an example of the filler, titanium oxide,
Calcium carbonate, magnesium carbonate, silica, metal oxides such as alumina, talc, chromates, ferrocyanides, various metal sulfates, sulfides, selenides, inorganic pigments such as phosphates, phthalocyanine-based, quinacridone-based, Isoindolinone-based, perinone-based, dioxazine-based organic pigments, carbon black, gold, silver,
Fine particles of metal or alloy such as copper, platinum, palladium, nickel, aluminum, silicon, brass, etc., metal powder whose surface is coated with a different kind of metal, colored filler in which pigment or dye is dispersed in fine particles formed of organic compound Etc. can be mentioned.

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 a high adhesiveness with the resin composition, and particularly when it is exposed on the resin plate surface, the resin plate surface may be modified because it reacts with the coupling agent. It 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 organic fine particles of natural products such as cellulose.

When the powder or particles used as the filler in the present invention has a wide particle size distribution, the filling factor becomes high when the coloring agent is contained in a high concentration, and thus the permeability of actinic rays is lowered. The shape of the colorant used in the present invention is not particularly limited, and may be any shape such as spherical, flat, or polyhedral. The content of the filler used in the present invention is preferably 4 in terms of curability with respect to 100 parts by weight of the resin composition.
It is 0 part by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less. Further, by incorporating the above-mentioned organic fine particles, particularly fluorine-based fine particles such as tetrafluoroethylene, the releasability from the hardened concrete can be improved. Further, by containing fine ceramic particles such as boron nitride, silicon nitride, or silicon carbide, the abrasion resistance of the resin plate can be improved.

In the resin plate for concrete formwork of the present invention, the thickness is 0.001 μm or more and 100 μm or less, preferably 0.0, between the sheet-shaped substrate and the photosensitive resin composition layer.
5 μm or more and 20 μm or less, more preferably 0.05 μm
An adhesive layer having a thickness of 10 μm or less can be inserted, and it has an effect of improving the adhesiveness between the sheet-shaped substrate and the photosensitive resin composition layer. The thickness of the adhesive layer is preferably 0.001 μm or more from the viewpoint of ensuring a sufficient adhesive force, and 100 μm or less from the viewpoint of suppressing warpage due to heat. The adhesive used when forming the adhesive layer is not particularly limited, and a thermosetting adhesive, a photocurable adhesive or the like that is commonly available can be used.

In the resin plate for concrete formwork of the present invention, the surface on the side where the convex pattern is formed can be modified by 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 having high reactivity with a surface hydroxyl group of a substrate, and such a functional group is, for example, a trimethoxysilyl group or triethoxysilyl group. Group, trichlorosilyl group, diethoxysilyl group, dimethoxysilyl group, dimonochlorosilyl group, monoethoxysilyl group, monomethoxysilyl group, monochlorosilyl group. Further, at least one or more of these functional groups are present in the molecule, and are immobilized on the surface of the base material by reacting with the surface hydroxyl groups of the base material. Further, the compound constituting the silane coupling agent of the present invention is selected from an acryloyl group, a methacryloyl group, an active hydrogen-containing amino group, an epoxy group, a vinyl group, a perfluoroalkyl group, and a mercapto group as a reactive functional group in the molecule. A compound having at least one functional group or a compound having a long-chain alkyl group can be used. The structure is not particularly limited,

As 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-
Methacryloxypropyl methyldiethoxysilane, 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-
Ureidopropyltriethoxysilane and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane

(D) Epoxy group-containing γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3.
4 Epoxycyclohexyl) ethyltrimethoxysilane (e) having vinyl group vinyltriethoxysilane, and vinyltrimethoxysilane (f) having mercapto group γ-mercaptopropyltrimethoxysilane, and γ-
Mercaptopropylmethyldimethoxysilane

(G) Having perfluoroalkyl group CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF
₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH
₃ (OCH ₃ ) ₂ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃ , CF
₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃

As the titanium coupling agent, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) is used. ) Titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (octylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl Titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoylditanate Kuriruchitaneto, isopropyl tri (dioctyl sulfate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) may include compounds such as titanates. The above coupling agent may be diluted with water-alcohol or acetic acid water-alcohol mixed solution, if necessary. The concentration of the coupling agent in the treatment liquid is preferably 0.05 to 10.0% by weight.

The coupling agent treatment method will be described.
The treatment liquid containing the above-mentioned coupling agent is applied to a resin plate for concrete formwork and used. The method of applying the coupling agent treatment liquid is not particularly limited, and for example, a dipping 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. Further, 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 prepared resin plate for concrete formwork is used by being attached to the surface of the concrete formwork via an adhesive layer. As the adhesive, a commonly available adhesive such as a double-sided adhesive sheet or a spray adhesive can be used. In particular, when the resin plate is used by reattaching it, it is necessary to easily remove it. Therefore, an adhesive sheet of the type that foams by heating and its adhesive strength becomes extremely small, for example, Nitto Denko's trademark "Riva" It is also effective to use "alpha".

As a method for evaluating the physical properties of hardened concrete, non-destructive inspection such as Schmidt hammer test is widely performed. This method is a method of hitting a steel ball on the surface of concrete, and is known as a method of estimating strength without breaking concrete. According to this method, the strength of concrete is indirectly estimated by utilizing the characteristics that concrete having high strength has a high degree of repulsion of steel balls and concrete having low strength has low degree of repulsion of steel balls. In the present invention, based on this method, a diameter of 10.9
A method was used in which a steel ball having a weight of 5.4 g and a weight of 5.4 g was dropped onto the concrete surface from a height of 30 cm, and the height at which the steel ball repelled was measured.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

[0054]

Example 1 [Production of prepolymer] Number average molecular weight 25
No. 00 polyoxyethylene (EO) -polyoxypropylene (PO) block copolymer diol (EO / PO molar ratio 1/4) 80 parts by weight and dibutyltin dilaurate as a catalyst 0.1 part by weight, 2,6-t 0.8 parts by weight of -butyl-4-methylphenol was placed in a reaction vessel and mixed with stirring. To this, 8.9 parts by weight of tolylene diisocyanate was added dropwise with stirring at an external temperature of 40 ° C., after which the external temperature was gradually raised and reacted at 80 ° C. for about 5 hours. Further, 11.5 parts by weight of 2-hydroxypropyl methacrylate was added and mixed well for about 2 hours. As a result, unsaturated polyurethane prepolymer a was obtained.

[Preparation of Photosensitive Resin Composition] For 80 parts by weight of unsaturated polyurethane prepolymer a, 16 parts by weight of ethylene glycol dimethacrylate, photopolymerization initiator 2,
0.4 parts by weight of 2-dimethoxy-2-phenylacetophenone and 0.05 parts by weight of a polymerization inhibitor 2,6-t-butyl-4-methylphenol were mixed to obtain a photosensitive resin composition A.

[Preparation of resin plate] A glass plate of a flexographic plate making machine, trademark "AWF plate making machine" manufactured by Asahi Kasei Co., Ltd., has a thickness of 1
A base film for a photosensitive resin plate, in which an adhesive having a thickness of several μm is applied to one surface of a transparent polyethylene terephthalate film having an thickness of 80 μm, was placed so that the surface to which the adhesive layer was applied faced up, and vacuum adhered. . On the base film, the photosensitive resin composition A was molded and spread to have a thickness of 2.5 mm by 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 laminating roller,
It is a traveling type spreading device with a bucket (resin reservoir), negative film, guides, etc. It is a photosensitive resin while running on a spacer (rail that moves up and down to regulate the plate thickness) along the glass surface. It is an apparatus that casts a composition and spreads (coats) a photosensitive resin composition layer to a predetermined thickness while feeding a negative film. The negative film has a transparent polyester film having a thickness of 120 μm coated with a heat-sensitive material on one side, and was previously designated by a user with CAD data using a thermal head printer (Ricoh Co., Ltd., trade name “thermal plotter”). It is a negative film of a resin plate for concrete formwork produced by outputting an image in which patterns and characters are input. Since the heat-sensitive material in contact with the thermal head turns black, the blackened portion of the negative film does not transmit high energy rays. The minimum size of this black light-shielding portion was 3 mm.

Next, the photosensitive resin composition A was cured by irradiating ultraviolet rays from the top 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, the negative film is peeled off, the uncured portion that is not irradiated with ultraviolet rays is scraped off with a spatula, and then the uncured portion is removed with a weak alkaline detergent (Asahi Kasei Co., Ltd., trade name "W-10"). Completely removed. Furthermore, the resin plate was completely cured by irradiating it with ultraviolet rays in water, and then the water was removed using a hot air dryer to obtain a resin plate for a concrete form. 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-shaped substrate having a thickness of 180 μm. The resin plate had a uniform thickness and its accuracy was within ± 10 μm. FIG. 1D shows this state.

The taper angle of the convex pattern formed on the surface of the sheet-shaped substrate was 83 °. Further, the thickness of the resin residual layer remaining on the portion other than the convex pattern on the surface of the sheet-shaped 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 base film made of polyethylene terephthalate, which is the sheet-shaped substrate, was 50 ppm as a result of measurement using a thermomechanical measuring device (Shimadzu Corporation, trade name "TMA-50").
/ ° C., and the melting temperature measured by a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name “DSC-60”) is 2
It was 45 ° C.

[Attachment to concrete formwork] A spray-type adhesive was applied to the surface of the resin plate for concrete formwork (a) obtained as described above on the side where no convex pattern was present, and iron concrete was applied. I attached it to the formwork.

[Transfer of pattern to concrete surface]
100 parts by weight of Poldland cement and 200 sand in the formwork
Fresh concrete consisting of 1 part by weight, 300 parts by weight of gravel, and 60 parts by weight of water was poured and heated in a steam bath at 70 to 75 ° C. for 4 hours, and then left to cool at room temperature for 30 minutes to cure the concrete. The hardened concrete is easily released from the metal mold, the surface of the obtained concrete is smooth, there are no deposits, and the photosensitive resin applied inside the mold is completely on the mold surface. It remained attached. On the surface of the hardened concrete, a concave pattern obtained by completely transferring the convex pattern of the resin plate was obtained. In addition, the height of the part where the concave pattern of the hardened concrete has the concave pattern is lower than the height specified by the dimensions of the formwork by the thickness of the sheet-shaped base material, and almost the standard product can be obtained. It was

[0061]

Example 2 [Production of prepolymer] thermometer, stirrer,
Trademark "PCD" which is a polycarbonate diol manufactured by Asahi Kasei Corporation in a 1 L separable flask equipped with a reflux condenser.
L L4672 "(number average molecular weight 1990, OH value 5
6.4) 100 parts by weight of tolylene diisocyanate 6.
After adding 9 parts by weight and reacting at 80 ° C. for about 3 hours under heating, 3.3 parts by weight of 2-methacryloyloxyisocyanate was added and further reacted for about 3 hours, and the terminal was a methacrylic group (intramolecular). To prepare a prepolymer b having a number average molecular weight of about 10,000 and having at least about 2 polymerizable unsaturated groups per molecule). This resin was syrup-like at 20 ° C., flowed when an external force was applied, and did not recover the original shape even when the external force was removed.

[Preparation of Photosensitive Resin Composition] With respect to 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, photopolymerization initiator 2, 0.4 parts by weight of 2-dimethoxy-2-phenylacetophenone, polymerization inhibitor 2,6-t-butyl-4-methylphenol 0.0
5 parts by weight, and further 5 parts by weight of finely divided silica having a number average particle diameter of 4.5 μm (trade name “CYLOSPHERE C-1504” manufactured by Fuji Silysia Chemical Ltd.) were mixed to obtain a photosensitive resin composition B. .

[Preparation of Resin Plate] The photosensitive resin 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 transparent polyester film having a thickness of 150 μm was used instead of the negative film. A sheet-like laminate was formed by laminating a cured product layer having a thickness of 2.5 mm, which substantially consisted only of a convex pattern of the composition. However,
Since the entire surface of the photosensitive resin composition layer is exposed, it is not necessary to remove the uncured portion.

Next, using a carbon dioxide gas laser engraving machine,
By digging up to the place where the sheet-shaped substrate is exposed, a convex pattern was formed on the photosensitive resin cured product layer of the sheet-shaped laminate. The laser engraving machine used is BAASE
L company, trademark "TYP STAMPLAS SN 0
It was 9 ". In this apparatus, a laser beam can be computer-controlled to faithfully form a pattern on the cured photosensitive resin layer according to CAD data. Through the above steps, a resin plate (a) for concrete formwork having a convex pattern formed on the surface of the sheet-shaped substrate was produced. The thickness of the resin residual layer remaining on the portion other than the convex pattern on the surface of the sheet-shaped substrate was 10 μm or less, and this value was 0.4% or less of the height of the convex pattern.

[Attaching to concrete formwork] A spray-type adhesive was applied to the surface of the resin plate for concrete formwork (a) obtained as described above on the side where the convex pattern does not exist, and iron concrete was applied. I attached it to the formwork.

[Transfer of pattern to concrete surface]
100 parts by weight of Poldland cement and 200 sand in the formwork
Fresh concrete consisting of 1 part by weight, 300 parts by weight of gravel, and 60 parts by weight of water was poured and heated in a steam bath at 70 to 75 ° C. for 4 hours, and then left to cool at room temperature for 30 minutes to cure the concrete. The hardened concrete is easily released from the metal mold, the surface of the obtained concrete is smooth, there are no deposits, and the photosensitive resin applied inside the mold is completely on the mold surface. It remained attached. On the surface of the hardened concrete, a concave pattern obtained by completely transferring the convex pattern of the resin plate was obtained. Further, the height of the portion of the hardened concrete where the concave pattern was present was only lower than the height defined by the dimensions of the mold by the thickness of the sheet-shaped substrate, and a product almost conforming to the standard was obtained.

[0067]

[Example 3] [Preparation of resin plate for concrete formwork] Same as Example 1 except that a 50 µm thick wholly aromatic polyamide film (trade name "Aramica" manufactured by Asahi Kasei) is used as a sheet-shaped substrate. Then, a resin plate (c) for concrete formwork was produced. The surface of the wholly aromatic polyamide film used as the sheet-shaped substrate was subjected to plasma treatment in order to improve the adhesion with the substrate to be laminated, and one side of the film had an epoxy adhesive with a thickness of several μm. Layers were formed. The coefficient of linear thermal expansion of the wholly aromatic polyamide film was 4 ppm / ° C. Furthermore, the heat distortion temperature is 25
It was 0 ° C or higher. The thickness of the resin residual layer remaining on the portion other than the convex pattern on the surface of the sheet-shaped substrate was 10 μm or less, and this value was 0.4% or less of the height of the convex pattern.

[Attachment to concrete formwork] A double-sided adhesive tape was attached to the surface of the resin plate for concrete formwork (C) prepared as described above on the side where the convex pattern was not formed, and the iron concrete formwork was attached. Pasted on.

[Transfer of pattern to concrete surface]
100 parts by weight of Poldland cement and 200 sand in the formwork
Fresh concrete consisting of 1 part by weight, 300 parts by weight of gravel, and 60 parts by weight of water was poured and heated in a steam bath at 70 to 75 ° C. for 4 hours, and then left to cool at room temperature for 30 minutes to cure the concrete. The hardened concrete is easily released from the metal mold, the surface of the obtained concrete is smooth, there are no deposits, and the photosensitive resin applied inside the mold is completely on the mold surface. It remained attached. On the surface of the hardened concrete, a concave pattern obtained by completely transferring the convex pattern of the resin plate was obtained. Further, the height of the portion of the hardened concrete where the concave pattern is present is only lower than the height defined by the dimensions of the formwork by the thickness of the sheet-like base material, and a product almost conforming to the standard was obtained. .

[0070]

[Example 4] [Production of resin plate for concrete formwork] A resin plate for concrete formwork (ii) was produced by the same method as in Example 2. The surface of the resin plate was modified by treating it with a silane coupling agent having a perfluoroalkyl group. Perfluoroalkyl group-containing silane coupling agent (GE Toshiba Silicone,
Trademark "TSL8233") 10 g, methanol 939
g, acetic acid 1 g, and water 50 g were stirred at room temperature (25 ° C.) for 1 hour to obtain a silane coupling agent treatment liquid.
This treatment liquid was uniformly and thinly applied to the surface of the resin plate for concrete form, and dried at 100 ° C. for 10 minutes. In this way, a resin plate (D) for concrete formwork was obtained. The thickness of the resin residual layer remaining on the portion other than the convex pattern on the surface of the sheet-shaped substrate was 10 μm or less, and this value was 0.4% or less of the height of the convex pattern.

[Attachment to concrete formwork] A double-sided adhesive tape is applied to the surface of the resin plate for concrete formwork (d) prepared as described above on the side where the convex pattern is not formed, and the iron concrete formwork is attached. Pasted on.

[Transfer of pattern to concrete surface]
100 parts by weight of Poldland cement and 200 sand in the formwork
Fresh concrete consisting of 1 part by weight, 300 parts by weight of gravel, and 60 parts by weight of water was poured and heated in a steam bath at 70 to 75 ° C. for 4 hours, and then left to cool at room temperature for 30 minutes to cure the concrete. The hardened concrete is easily released from the metal mold, the surface of the obtained concrete is smooth, there are no deposits, and the photosensitive resin applied inside the mold is completely on the mold surface. It remained attached. On the surface of the hardened concrete, a concave pattern obtained by completely transferring the convex pattern of the resin plate was obtained. Further, the height of the portion of the hardened concrete where the concave pattern is present is only lower than the height defined by the dimensions of the formwork by the thickness of the sheet-like base material, and a product almost conforming to the standard was obtained. .

A test was carried out in which the surface of the concrete taken out from the formwork was hit with a hammer.
Although several recesses with a size of less than mm were generated, no cracks were generated. The material of the hammer used was steel, the surface to be lowered was a plane, a circle having a diameter of about 50 mm, and the weight was about 2 kg. This hammer is about 30
From the point of cm, the same place on the concrete surface was hit 5 times by a method of dropping by gravity without applying force.

On the concrete surface, a diameter of 10.9
A steel ball having a size of mm and a weight of 5.4 g was dropped from a height of 30 cm, and the height at which the steel ball repelled was measured and found to be 10 cm. Furthermore, the metal mold was repeatedly used without applying the mold release agent, but the mold was still smoothly released after 10 times of repeated use, and the surface of the obtained concrete was smooth, and There were no deposits. Further, it was found that rust did not occur on the surface of the mold and that it had a rust preventive effect.

[0075]

[Example 5] The same photosensitive resin composition B as in Example 2 was prepared, and the average thickness of the photosensitive resin composition was 0.2 mm without digging with a carbon dioxide laser until the surface of the sheet-shaped substrate was exposed. A resin plate having a convex pattern formed on the surface of the sheet-shaped substrate was produced in the same manner as in Example 2 except that the laser processing was stopped when the cured resin layer was left. That is, a thickness of 180 μm with an adhesive layer of several μm on the surface
Has a convex pattern with a height of about 2.3 mm formed on the surface of the sheet-shaped substrate, and the photosensitive resin cured material layer has an average value of 0.2 mm at the bottom of the concave portion other than the convex pattern portion.
It is the remaining resin plate. The thickness of the resin residual layer was 8.7% of the height of the convex pattern.

Next, in the same manner as in Example 4, 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 give a resin plate for concrete form ( Oh) Further, in the same manner as in Example 1, the resin plate (e) was attached to the surface of the concrete form, and the pattern on the surface of the resin plate was transferred to the concrete surface. The hardened concrete is easily released from the metal mold, the surface of the obtained concrete is smooth, there are no deposits, and the photosensitive resin applied inside the mold is completely on the mold surface. It remained attached. On the surface of the hardened concrete, a concave pattern obtained by completely transferring the convex pattern of the resin plate was obtained. Further, the height of the portion of the hardened concrete where the concave pattern is present is equal to the thickness of the sheet-shaped substrate and the thickness of the remaining cured photosensitive resin layer, that is, 0 from the height defined by the dimensions of the mold. Only a low value of 38 mm was obtained, and a product almost conforming to the standard was obtained.

A test was carried out in which the surface of the concrete taken out from the formwork was hit with a hammer.
Although several recesses with a size of less than mm were generated, no cracks were generated. The material of the hammer used was steel, the surface to be lowered was a plane, a circle having a diameter of about 50 mm, and the weight was about 2 kg. This hammer is about 30
From the point of cm, the same place on the concrete surface was hit 5 times by a method of dropping by gravity without applying force.

The diameter of the concrete surface was 10.9.
A steel ball having a size of mm and a weight of 5.4 g was dropped from a height of 30 cm, and the height at which the steel ball repelled was measured and found to be 10 cm. Furthermore, the metal mold was repeatedly used without applying the mold release agent, but the mold was still smoothly released after 10 times of repeated use, and the surface of the obtained concrete was smooth, and There were no deposits. Further, it was found that rust did not occur on the surface of the mold and that it had a rust preventive 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 its surface, and hot pressed to transfer the pattern of the mold to the natural rubber plate. The height of the convex pattern of the rubber plate to which the pattern is transferred is 2.5 m
The thickness of the base portion, that is, the portion having no pattern was 1.5 mm. Further, as a result of measuring the thickness at the portion of the convex pattern, there was partial thickness unevenness, and the plate thickness accuracy was about ± 0.2 mm. It is presumed that this is because the rubber composition is less likely to fluidize during hot pressing.

[Attachment to Concrete Form] A double-sided adhesive tape was attached to the surface of the natural rubber plate prepared as described above on the side where the convex pattern was not formed, and attached to an iron concrete form.

[Transfer of pattern to concrete surface]
A release agent made of mineral oil is applied to the surface of the rubber plate, and 100 parts by weight of Poldland cement, 200 parts by weight of sand, 300 parts by weight of gravel, and 60 parts by weight of water are poured into the mold, and 70- After heating in a steam bath at 75 ° C. for 4 hours, it was allowed to cool at room temperature for 30 minutes to cure the concrete. A concave pattern obtained by transferring the convex pattern of the rubber plate was obtained on the hardened concrete surface. Also,
The height of the part of the hardened concrete with the concave pattern is 1.5 mm lower than the height specified by the dimensions of the formwork by the thickness of the base of the rubber plate, and it cannot be said that the standard is met. It has become a product. Hardened concrete has a very poor releasability from the metal mold,
Part of the molded concrete was chipped off, or concrete adhered to the formwork.

As in Example 4, a test was performed in which the surface of the concrete taken out from the mold was hit with a hammer. As a result, numerous recesses having a depth of several mm were generated and cracks were also confirmed. Also, on the concrete surface, the diameter of 10.9
A steel ball having a size of mm and a weight of 5.4 g was dropped from a height of 30 cm, and the height at which the steel ball repelled was measured and found to be 4 cm.

[0083]

[Comparative Example 2] As a sheet-shaped substrate, a linear thermal expansion coefficient of 150
A resin plate (F) for concrete formwork was produced in the same manner as in Example 1 except that a polyethylene film having a ppm / ° C, a melting temperature of 135 ° C and a thickness of 150 µm was used.

[Attachment to Concrete Formwork] A double-sided adhesive tape was attached to the surface of the resin plate for concrete formwork (F) prepared as described above on the side where the convex pattern was not formed, and the iron concrete formwork was attached. Pasted on.

[Transfer of pattern to concrete surface]
A release agent made of mineral oil is applied to the surface of the rubber plate, and 100 parts by weight of Poldland cement, 200 parts by weight of sand, 300 parts by weight of gravel, and 60 parts by weight of water are poured into the mold, and 70- After heating in a steam bath at 75 ° C. for 4 hours, it was allowed to cool at room temperature for 30 minutes to cure the concrete. Although a concave pattern obtained by transferring the convex pattern of the resin plate was obtained on the surface of the hardened concrete, 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 the deformation of the resin plate was several mm at a large place. Further, the surface of the hardened concrete has a partly recessed portion, which causes a problem in height uniformity.

[0086]

Comparative Example 3 A concrete resin plate (g) was obtained in the same manner as in Example 1 except that the minimum size of the black light-shielding portion of the negative film was 0.2 mm. In this resin plate (g), the thickness of the resin residual layer remaining in the portion other than the convex pattern on the surface of the sheet-shaped substrate at the portion corresponding to the minimum dimension of 0.2 mm of the light-shielding portion of the negative film is 1 It was 0.5 mm, which was 60% of the height of the convex pattern. However, in the part where the size of the light shielding part is larger than 3 mm,
The thickness of the resin residual layer was 10 μm or less, and this value was 0.4% or less of the height of the convex pattern. Therefore, in the light-shielding portion of the negative film, a large difference occurred in the thickness of the resin residual layer between the small-sized portion and the large-sized portion.

[Attachment to concrete formwork] A double-sided adhesive tape was attached to the surface of the resin plate for concrete formwork (F) prepared as described above on the side where the convex pattern was not formed, and the iron concrete formwork was attached. Pasted on.

[Transfer of pattern to concrete surface]
A release agent made of mineral oil is applied to the surface of the rubber plate, and 100 parts by weight of Poldland cement, 200 parts by weight of sand, 300 parts by weight of gravel, and 60 parts by weight of water are poured into the mold, and 70- After heating in a steam bath at 75 ° C. for 4 hours, it was allowed to cool at room temperature for 30 minutes to cure the concrete. The pattern of the resin plate (ki) was faithfully transferred to the surface of the concrete taken out from the formwork, but the depth of the recess transferred to the concrete side varies greatly depending on the size of the light-shielding part of the negative film. , Was out of specifications for the designed dimensions.

[0089]

EFFECTS OF THE INVENTION According to the present invention, dimensional accuracy is high, mold releasability is excellent, and a concavo-convex pattern that faithfully copies the pattern of a resin plate can be formed on the surface of concrete, and it can be repeatedly used and has excellent durability. Further, it is possible to provide a resin plate for a concrete mold having a high dimensional stability, in which the surface of the hardened concrete is hard, and the period until it is completely hardened after being taken out from the mold is shortened, and a method for forming the same.

[Brief description of drawings]

FIG. 1 is a diagram showing a method for producing a resin plate of an example of the present invention, and (a), (b), (c) and (d) are explanatory diagrams showing a production 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-shaped base material.

[Explanation of symbols]

1 Sheet-shaped substrate 2 Photosensitive resin composition layer 3 Negative film 4 Cured product of photosensitive resin composition W Conventional base plate thickness R Tapered angle of convex pattern

Claims (9)

[Claims] 1. A resin plate comprising a sheet-shaped base material and a photosensitive resin cured product layer having a convex pattern, which is mounted on a surface of a concrete formwork and is used, wherein the sheet-shaped base material has a thickness of 0. 01 mm or more and 1 mm or less, and a linear thermal expansion coefficient of 10
0 ppm / ° C. or less, the convex pattern of the cured photosensitive resin is 0.01 mm or more and 50 mm or less in height, and the thickness of the resin residual layer in the portion where the convex pattern does not exist is 10% of the convex pattern. The following resin plates for concrete formwork. 2. The resin plate for concrete formwork according to claim 1, wherein the sheet-shaped substrate has a melting temperature of 150 ° C. or higher. 3. An unsaturated polyurethane prepolymer having a photosensitive resin cured product, which comprises (A) a plurality of diol segments bonded via urethane bonds and has an ethylenically unsaturated group at at least one terminal (B). The resin plate for concrete formwork according to claim 2, which is a cured product of a resin composition containing at least one or more reactive monomers having an ethylenically unsaturated bond and (C) a photopolymerization initiator. . 4. The cured product of the photosensitive resin has a number average particle diameter of 0.
The resin plate for concrete formwork according to claim 1, which contains a filler of 1 μm or more and 100 μm or less. 5. The resin for concrete formwork according to claim 1, wherein an adhesive layer having a thickness of 0.001 μm or more and 100 μm or less is present between the sheet-shaped base material and the cured photosensitive resin layer. Edition. 6. A photosensitive resin composition layer is provided on the surface of a sheet-shaped base material having a thickness of 0.01 mm or more and 1 mm or less, and a negative film for providing a convex pattern is further spread on the photosensitive resin composition layer, and a negative film A height of 0.01 mm on the sheet-shaped substrate is obtained by irradiating the composition with an energy ray to cure the composition and removing the uncured portion not exposed to the high energy ray.
For a concrete formwork, characterized in that a convex pattern of a cured photosensitive resin of 50 mm or less is formed, and the thickness of the resin residual layer without the convex pattern is 10% or less of the convex pattern. Resin plate manufacturing method. 7. The method according to claim 6, wherein the surface of the photosensitive resin cured product on the side where the convex pattern is present is treated with a treatment liquid containing a coupling agent. 8. A photosensitive resin composition layer is provided on the surface of a sheet-shaped substrate having a thickness of 0.01 mm or more and 1 mm or less, and the entire surface of the liquid photosensitive resin layer is irradiated with high energy rays to obtain the photosensitivity. By curing the resin layer and further removing the photosensitive resin cured layer by irradiating a laser, a convex pattern of the cured photosensitive resin having a height of 0.01 mm or more and 50 mm or less is formed on the sheet-shaped substrate. A method for producing a resin plate for concrete formwork, characterized in that the thickness of the resin residual layer formed and having no convex pattern is 10% or less of the convex pattern. 9. A concrete formwork obtained by mounting the resin plate according to claim 1 on the surface of a concrete formwork via an adhesive layer.