JPH1149833A - Putty composition for concrete structure and its hardening - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a putty composition hardly causing danger by a treatment of a dangerous material and trouble in the using time, and capable of being hardened in a short time by including a polymerizable unsaturated compound, a filler, an acidic compound and a polymerization initiator comprising a specific organic boron compound. SOLUTION: This putty composition comprises (A) 100 pts.wt. polymerizable unsaturated compound (e.g. an unsaturated polyester resin and a vinyl ester resin) (B) 10-300 pts.wt. filler, (C) an acidic compound and a polymerization initiator comprising an organic boron compound of formula I (R<1> to R<4> are each a (substituted) alkyl, aryl, aralkyl, alkenyl, alkynyl or silyl, or a heterocycle or a halogen; Z<+> is a cation), preferably hexaarylbiimidazole of formula II [L<1> to L<3> are each a (substituted) aryl], and preferably (D) a visible light polymerization initiator (e.g. acylphosphine oxide-based compound).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a putty composition for concrete used for lining or coating a cement mortar or a concrete layer of a building in the field of construction and civil engineering, and a method of curing the same. In addition, the putty composition for concrete is characterized in that it can be cured in a short time by light irradiation, and that a part that cannot be sufficiently irradiated with light can be cured by a dark reaction.

[0002]

2. Description of the Related Art When lining or coating a surface of a building such as concrete with an unsaturated polyester resin or a vinyl ester resin, the surface is unsaturated for the purpose of flattening irregularities on the concrete surface. A polyester resin putty, a vinyl ester resin putty, or an epoxy resin putty is used.
Normally, these putty compositions require room temperature cured putty with peroxide catalyst such as unsaturated polyester resin or vinyl ester resin, or cured putty of epoxy resin. Work efficiency is poor. In addition, such a room-temperature-curable composition requires a curing agent to be mixed with the resin on site, causing troubles in adjusting the pot life and causing an explosion due to handling of peroxide. In addition, volatile reactive monomers (such as styrene monomer) volatilize, causing air pollution at the work site, or reducing the primer performance due to a change in the mixing ratio of the resin composition, causing a risk of loss of resin and ignition. And other problems.

[0003] As means for solving these drawbacks, on-site environmental pollution and curability have been improved by replacing volatile monomers mixed with the putty composition with other high-boiling compounds. It takes a long time to completely cure a room temperature curing system with a saturated polyester resin or vinyl ester resin-based peroxide catalyst or a curing system of an epoxy resin. Problems such as pot life problems cannot be solved.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is a putty which can be cured in a short time without danger or trouble in pot life caused by handling a dangerous substance such as a peroxide catalyst on site. The aim is to develop compositions and their curing methods.

[0005]

The present invention provides: [1] (A) 100 parts by weight of a polymerizable unsaturated compound; (B) 10 to 300 parts by weight of a filler; A putty composition for a concrete structure, comprising a polymerization initiator comprising an organoboron compound represented by 1),

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, A substituted aryl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a cation. [2] (A) Polymerizable unsaturated compound: 100 parts by weight, (B) filling Material: 10 to 300 parts by weight, (C) a polymerization initiator comprising an acidic compound and an organoboron compound represented by the general formula (1), and (D) a putty composition for concrete construction containing a visible light polymerization initiator. [3] The putty composition according to the above [2], wherein the visible light polymerization initiator is an acylphosphine oxide compound.

[4] (A) Polymerizable unsaturated compound: 100
Parts by weight, (B) filler: 10 to 300 parts by weight, (C) polymerization comprising an acidic compound, an organic boron compound represented by the general formula (1), and a hexaarylbiimidazole represented by the general formula (2). A putty composition for a concrete structure containing an initiator,

Embedded image (In the formula, L ¹ , L ² and L ³ each independently represent an aryl group or a substituted aryl group.) [5] (A) 100 parts by weight of a polymerizable unsaturated compound, (B) filler: 10 to 10 parts by weight 300 parts by weight, (C) a polymerization initiator comprising an acidic compound, an organic boron compound represented by the general formula (1) and a hexaarylbiimidazole represented by the general formula (2), and (D) a visible light polymerization initiator A putty composition for a concrete structure containing

[6] The putty composition according to any one of the above [1] to [5], wherein the polymerizable unsaturated compound is an unsaturated polyester resin, a vinyl ester resin and / or an acrylic resin. The putty composition according to any one of the above [1] to [6], wherein the material is an inorganic and / or organic filler; [8] the acidic compound is maleic acid, fumaric acid or a half ester thereof (anhydrous) The putty composition according to any one of the above [1] to [7], selected from at least one of polymerizable unsaturated compounds such as, (meth) acrylic acid and itaconic acid or oligomers or polymers containing these acidic compounds. [9] The above-mentioned [1] to [1], wherein the acidic compound is a latent acid generator that generates an acid by light irradiation and / or heating.
[10] The putty composition according to any of [9], wherein the latent acid generator is an organic sulfonium compound,

[11] A method for curing the putty composition, wherein the putty composition according to any one of the above [1] to [10] is cured by light irradiation and / or heating, and [12] a light source for light irradiation. However, by developing the method for curing the putty composition according to the above [11], which is a light source that emits light having a wavelength in the visible light and / or near-infrared light range, the method can be performed safely without using a peroxide catalyst. No trouble in using time,
The above object was solved by enabling curing in a short time and also in a part where light is hardly transmitted through a dark reaction. In addition, since the putty composition can be made into a one-part type or a safe two-part mixing type that can be mixed one-on-one, workability can be improved safely without any trouble.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin used in the present invention includes an unsaturated polyester resin and a vinyl ester resin (hereinafter, both resins may be collectively referred to as a resin or the like).
Use at least one of them. The unsaturated polyester as a raw material of the unsaturated polyester resin may be one produced by a known method, and specifically, polymerization of phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, etc. An unsaturated polybasic acid having no unsaturated bond or an anhydride thereof and an unsaturated polybasic acid having an active unsaturated bond such as fumaric acid, maleic anhydride, maleic acid, itaconic acid or an anhydride thereof or an acid component thereof. And ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1, 3-propanediol, 2,2
Manufactured by reacting a polyhydric alcohol such as -dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A as an alcohol component. It is.

[0010] The vinyl ester as a raw material of the vinyl ester resin (epoxy acrylate resin) is produced by a known method. The epoxy resin is reacted with an unsaturated monobasic acid such as acrylic acid or methacrylic acid. Α, β to the epoxy (meth) acrylate obtained by the above method or the saturated or unsaturated polyester having a terminal carboxyl group obtained from a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyhydric alcohol.
A polyester (meth) acrylate of a saturated polyester or unsaturated polyester obtained by using an epoxy compound having an unsaturated carboxylic acid ester group as a component. Examples of the epoxy resin as a raw material include bisphenol A glycidyl ether, its high molecular weight homologues, and novolak type polyglycidyl ethers.

Examples of the saturated dicarboxylic acid used for the terminal carboxyl polyester include dicarboxylic acids having no active unsaturated group, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid and sebacic acid. Examples of the unsaturated dicarboxylic acid include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, and itaconic acid. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, -Methyl-1,3-
Propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol,
Polyhydric alcohols such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A are exemplified. As an epoxy compound containing an α, β-unsaturated carboxylic acid ester group used for producing a vinyl ester, glycidyl methacrylate is a typical example.

As the unsaturated polyester or vinyl ester used for the resin or the like, those having a relatively high degree of unsaturation are preferable, and those having an unsaturated group equivalent (molecular weight per unsaturated group) of about 100 to 800 are used. . Those having an unsaturated group equivalent of less than 100 cannot be synthesized. However, if the unsaturated group equivalent exceeds 800, a cured product having high hardness cannot be obtained.

The unsaturated polyester resin or vinyl ester resin used in the present invention is usually a mixture of the above unsaturated polyester or vinyl ester with a reactive monomer such as a styrene monomer.
The reactive monomer blended in the resin or the like of the present invention increases the kneadability and impregnation with a fiber material, a pigment, a filler, and the like when manufacturing a composite material, and the hardness, strength, and chemical resistance of a molded product. This is important for improving the water resistance and the like. The amount of the reactive monomer is 10 to 250 parts by weight based on 100 parts by weight of the unsaturated polyester and / or vinyl ester.
Parts by weight, preferably 20 to 100 parts by weight. If the amount is less than 10 parts by weight, the resin or the like has a high viscosity, which makes it difficult to construct the resin. On the other hand, if the amount exceeds 250 parts by weight, a high-strength product cannot be obtained, which is not preferable as a putty material. In this case, some or all of the styrene monomer may be replaced with another polymerizable monomer such as chlorostyrene, methyl methacrylate, and ethylene glycol dimethacrylate within a range that does not impair the gist of the present invention, and used.

The filler used in the present invention is an inorganic filler, an organic filler or a polymer. As the inorganic filler, for example, known ones such as aluminum hydroxide, calcium carbonate, talc, clay, glass powder, silica, barium sulfate, titanium oxide, and cement can be used. Of course, these inorganic fillers can be used in combination, and the amount used is 10 to 300 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of the polymerizable unsaturated compound. 300 inorganic fillers
If the amount is more than the weight part, the viscosity is too high and the workability is reduced, and the foam is apt to remain and the strength is reduced. When the amount of the inorganic filler is less than 10 parts by weight, a putty composition having good workability cannot be obtained. Further, in the present invention, thixotropic may be imparted by a known method. As the thixotropic agent, for example, 0.1 to 50 parts by weight of silica powder (aerosil type), mica powder, calcium carbonate powder and the like are added. There are methods.

The organic boron compound used in the present invention includes the following general formula (1)

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, Substituted aryl group, substituted allyl group,
Represents a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a cation)
It is represented by

Examples of the cation “Z ⁺ ” include quaternary ammonium cations, quaternary pyridinium cations, quinolinium cations, diazonium cations, and tetrazonium cations, which are insensitive to visible light and near-infrared light. Ions, phosphonium cations, (oxo) sulfonium cations, metal cations such as sodium, potassium, lithium, magnesium, and calcium, and cations on oxygen atoms such as flavylium and pyranium salts (organic)
Examples include compounds, carbon cations such as tropinium and cyclopropylium, halogen cations such as iodonium, and cations of metal compounds such as arsenic, cobalt, palladium, chromium, titanium, tin and antimony.

The acidic compounds used in the present invention include:
For example, inorganic acids generally known as Bronsted acids, such as hydrochloric acid, sulfuric acid, nitric acid, and organic acids such as acetic acid, propionic acid, maleic acid, adipic acid, (meth) acrylic acid, benzoic acid, and phthalic acids Examples include carboxylic acids, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. In addition, compounds containing a hydroxyl group such as phenols and alcohols, compounds having a mercapto group such as various thiols, and substances capable of forming a covalent bond by receiving an electron pair known as a Lewis acid, such as aluminum chloride, stannic chloride, and trichloride Boron, boron tribromide, or the like can be used. These acids are described in detail in, for example, "Organic Chemistry", 3rd edition, page 43, by Morrison Boyd. In addition, a substance having an acidic active site on a solid surface such as an acidic ion exchange resin, carbon black, and alumina, or an acidic gas compound such as hydrogen chloride and sulfurous acid gas can also be used.

Among these acidic compounds, (anhydride) maleic acid, fumaric acid, or a half ester thereof,
An acidic compound having a polymerizable unsaturated group such as (meth) acrylic acid and itaconic acid, or an oligomer or polymer having such a functional group is preferably used.
Furthermore, compounds that themselves are not acidic substances, but compounds that decompose or react by the action of heating, moisture in the air, oxygen or the like to generate acidic compounds also fall under the latent acidic compound of the present invention. Substances that generate an acidic compound by being decomposed by light irradiation are also known. For example, a compound called a photocationic polymerization initiator also corresponds to the photolatent acidic compound of the present invention. Various compounds such as diazonium compounds, sulfonium compounds, iodonium compounds, and metal complex compounds are known as photocationic initiators.
A detailed description can be found in October 1985, section 5, "Applications and Markets of UV / EB Curing Technology", page 78, published by CMC Corporation, 1989. Among these compounds to be referred to as latent acidic compounds, compounds that generate an acid by light or heat are desirable in view of availability, economy, stability in a composition, operability, and the like. An organic sulfonium compound which generates an acid by heating, and which is decomposed by heating to generate an acid is more preferable.

The organic sulfonium compound generally comprises an ion pair of a sulfonium cation moiety having three substituents (such as an alkyl group and an aryl group) and an anion as a counter ion. It is preferable that at least one of the substituents of the sulfonium salt is an aryl group such as a (substituted) phenyl group or a (substituted) naphthyl group from the viewpoint of the ability to generate an acidic compound, the acid strength of the generated acidic compound, and the like. For example, preferred compounds include sulfonium compounds having a cation moiety such as triphenylsulfonium and diphenylsulfonium. When the potable life of the resin composition containing the initiator is sufficiently required, for example, it is not preferable that the organic boron compound and the acidic compound come into contact with each other at the time of compounding the initiator. As the compound, it is desirable to use a compound that generates an acid by stimulus such as heat or light. It is also an effective means to use the putty composition in a two-liquid type of an organic boron compound mixture and an acidic compound mixture.

When a combination of an organic boron compound and an acidic compound is combined with a visible light initiator or a hexaarylbiimidazole compound to irradiate light, curing is further accelerated and a remarkable effect is obtained. As a visible light polymerization initiator having photosensitivity in the visible light region, for example, Yamaoka and the like, "surface", 27,
(7), 548 (1989), Sato et al., "Abstracts of the 3rd Polymer Material Forum", IBP18 (1994)
In addition to a single visible light polymerization initiator such as camphorquinone, benzyltrimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, dicyclopentadienyltitanium-di (pentafluorophenyl), organic peroxides / dye systems, Hexaarylbiimidazoles described in JP-B-45-37377, such as diphenyliodonium salts / dyes, imidazole / keto compounds, hexaarylbiimidazole compounds / hydrogen donating compounds, mercaptobenzothiazole / thiopyrylium salts, metal arenes / cyanine dyes, etc. / A known composite initiator system such as a radical generator.

A known bis (2,6-dimethoxybenzoyl)-having photosensitivity from ultraviolet light to visible light region.
2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -methylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide An acylphosphine compound such as For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 117)
3, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba-Geigy) 75% /
Trade name “IRGACURE 170” mixed at a rate of 25%
0 (manufactured by Ciba-Geigy Corporation), 1-hydroxy-cyclohexyl-phenyl ketone (trade name: "Irgacure 1")
84 "(manufactured by Ciba-Geigy) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba-Geigy).
Trade name “Irgacure 1800” (manufactured by Ciba Geigy) mixed at a ratio of 5% / 25%, 50% / 50%
"IRGACURE 1850" mixed in the ratio of
(Manufactured by Ciba Geigy Corporation), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name “Irgacure 819”), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Lucirin TPO BASF) 2)
-Hydroxy-2-methyl-1-phenylpropane-1
-One (trade name: Darocur 1173, manufactured by Ciba Geigy Corporation) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxyoxide (trade name: Luci)
Product name: “Darocur4265” mixed with 50% / 50% rinTPO BASF Co., Ltd.
and so on. 380 nm to 7 as visible light polymerization initiator
Any photopolymerization initiator having photosensitivity in the wavelength region of 80 nm may be used, and these may be used in combination.

As the hexaarylbiimidazole compound represented by the general formula (2), specifically, bis (2,4,4)
5-triphenyl) imidazole, bis (2-o-chlorophenyl-4,5-diphenyl) imidazole, bis (2-o, p-dichlorophenyl-4,5-diphenyl) imidazole, bis (2-o-bromophenyl-
4,5-diphenyl) imidazole and the like. The hexaarylbimidazole compound is described in detail in JP-B-41-3545.

A polymerization initiator obtained by combining an organic boron compound with a (latent) acidic compound and / or a visible light polymerization initiator, an organic boron compound and a (latent) acidic compound and / or
The optimal amount of the initiator combined with hexaarylbiimidazole varies depending on the type, amount, thickness and the like of the resin or the like, but is generally 0.1 to 100 parts by weight of the resin or the like.
It is 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight. If the amount of the polymerization initiator composition is less than 0.01 part by weight, the polymerization tends to be insufficient, and if the amount exceeds 20 parts by weight, it is economically disadvantageous and the physical properties of the cured product are deteriorated. When the resin or the like contains an acidic compound in advance, maleic acid, fumaric acid, or their half esters, (meth) acrylic acid, (anhydrous) contained in unsaturated polyester resin or vinyl ester resin,
Itaconic acid may be an oligomer or polymer having a carboxyl group of the carboxylic acid at the terminal,
Further, the resin may be in a form in which an arbitrary acidic compound is added to a resin or the like. In this case, the acid value of the unsaturated polyester resin or vinyl ester resin is 0.1 to 100 mg.
KOH / g, preferably 5 to 50 mgKOH / g.

The composition ratio of the organic boron compound to the (latent) acidic compound in the polymerization initiator is 0.1 / 5 to 5 /
0.1, preferably 0.5 / 5 to 5 / 0.5. When the ratio of the organic boron compound and / or the latent acidic compound is too small, the dark reaction cannot be sufficiently performed, and when the ratio of the organic boron compound and / or the latent acidic compound is too large, the economy becomes low. This is disadvantageous in terms of physical properties, and causes deterioration in physical properties of the cured product.

When an organic boron compound and an acidic compound are combined with a visible light polymerization initiator or hexaarylbiimidazole for further rapid curing, the ratio of the organic boron compound / visible light polymerization initiator or hexaarylbiimidazole is as follows. 0.1 / 5 to 5 / 0.1 by weight ratio,
Preferably it is 0.5 / 5 to 5 / 0.5. If the ratio of the visible light polymerization initiator or hexaarylbiimidazole is too small, the effect does not appear. If the ratio is too large, it is economically disadvantageous and the pot life under visible light is short. And the physical properties of the cured product are reduced.
If the initiator components of the organic boron compound and the acidic compound are small, the putty composition cannot sufficiently proceed the dark reaction. In the present invention, it goes without saying that a known radical generator such as an organic peroxide or an azo compound can be added for adjusting the curing.

In the present invention, a silane coupling agent may be added, if necessary, to improve the adhesion on the wet concrete surface. As a silane coupling agent, if necessary, use a moisture absorbent such as molecular sieve,
There is a method of adding 0.1 to 2 to 0 parts by weight of 3-methacryloxypropyltrimethoxysilane, vinylitrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, etc. to 100 parts by weight of the resin. . A detailed description is given in JP-A-6-271373.

In the present invention, visible light is 380-78.
Fig. 3 shows a light ray in a wavelength region of 0 nm. The light source used in the molding method of the present invention may be any light source that emits light in a wavelength range of 380 to 780 nm and generates heat, such as a metal halide lamp, a xenon lamp, a near-infrared light lamp, and a sodium lamp. , Halogen lamps, incandescent lamps, sunlight lamps, sunlight and the like can be used. Further, various lamps can be used in combination. Also,
In order to obtain a faster curing speed, light in a short wavelength region having a high energy order is effective, but it is difficult to completely cure the paste composition when the thickness is large. In this case, it is effective to irradiate light from a light source having a wavelength of 380 nm or more, which has a large distribution in a long wavelength region and generates heat, such as a metal halide lamp, a halogen lamp, a near-infrared lamp, and an infrared lamp. The light irradiation time varies depending on the effective wavelength of the light source, the output, the thickness of the composition, the amount of the filler, the amount of the polymerization initiator, and the like. It may be adjusted so as to be 0.05 hours or more.

In the putty composition for concrete and the method for curing the same according to the present invention, the resin composition to which the polymerization initiator is added by combining an organic boron compound with an acidic compound and / or a visible light polymerization initiator is used. It has a long life and is safe with no problem on the pot life, and if light is applied when it is desired to cure, the part that transmits visible light cures quickly and the part that does not easily transmit light reacts with the organic boron compound and the acidic compound. The curing progresses, and the gentle heat generated by the light source allows complete hardening of the portion where visible light is hardly transmitted, so that workability can be improved safely without any trouble. As a result, the molded body can be cured by solving the problem of deterioration of the working environment and the problem of the pot life due to the volatilization of the reactive monomer, and it is possible to cure, and it is economical, and the light used for polymerization is safe for humans. A light source that generates both visible light and heat is sufficient. Also, since the putty composition can be a one-pack type or a safe two-pack mixing type that can be mixed one-on-one, workability can be improved safely without any trouble at the work site.

[0029]

The present invention will be described in detail with reference to the following examples and comparative examples. In each example, "parts" and "%" are based on weight. (Example 1) (Pate composition) Vinyl ester resin [trade name: Lipoxy R
F-304X: manufactured by Showa Polymer Co., Ltd.]: 100 parts of a thixotropic agent fine particle silica [trade name: CAVOSIL TS-720:
USA, manufactured by Cabot Corp.]: 5 parts, aluminum hydroxide powder [trade name: Heidilite HBT-320, manufactured by Showa Denko KK]: 130 parts, boron compound: tetra-n-butylammonium triphenyl-n -Borate [manufactured by Showa Denko KK: hereinafter abbreviated as P3B]: Putty A prepared by mixing 0.5 part as a 40% solution of N-methylpyrrolidone
Except that P3B in Putty A: 0.5 part of N-methylpyrrolidone 40% was replaced by 2.0 parts of maleic acid type oligomer [trade name: MK-1, manufactured by Showa Polymer Co., Ltd.] Was putty B having exactly the same composition. (Conditions for applying and curing the primer) A room temperature-curable primer [trade name, CP-819B, manufactured by Showa Polymer Co., Ltd.] and methyl ethyl ketone peroxide [trade name Permec N, manufactured by NOF Corporation]: 1.2 parts 30cm
The upper surface (30 cm x 30 cm x 6 cm) of a concrete sidewalk board
cm × 30cm) with a brush (0.1kg / m ² )
And cured and dried for half a day.

(Applying and Curing of Putty) Next, for the purpose of controlling unevenness, a putty composition in which putty A and putty B were mixed in a ratio of 50 parts / 50 parts was thinly applied (0.8 kg / m ² ). hand,
2K which is a light source including a wavelength range of 380 to 1200 nm
W metal halide lamp [trade name: Dynabeam 2, manufactured by Toshiba Lighting & Technology Corp .; When light irradiation was performed for 10 minutes at a distance of 1 m using the above method, the surface became tack-free and cured. (FRP lining) Next, 2 ply of carbon fiber sheet (trade name: Tow Sheet, manufactured by Tonen Co., Ltd.) was added to Permec N, a room temperature curing catalyst [produced by NOF Corporation / cobalt naphthenate (cobalt 6%) = 1.5] Parts / 0.5 parts of vinyl ester resin (trade name: Lipoxy R-804, manufactured by Showa High Polymer Co., Ltd.) with a carbon content of 60 vol.
%, And laminated on a putty cured surface and left to cure for one day. (Adhesion test) ADHE to confirm putty performance
When the bonding strength and the state of breakage were examined with a bonding area of 4.9 cm ² using a SION TESTER elcometer, the concrete was peeled off by about 5 mm when the concrete base material was broken. The adhesion was good, and it was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength.

(Example 2) (Pate composition) Lipoxy RF-304X: 100 parts, thixotropic agent fine particle silica powder (trade name: Egilel # 200, manufactured by Nippon Aerosil Co., Ltd.): 5 parts, calcium carbonate [trade name: Softon 1200, manufactured by Bihoku Powder Chemical Industry Co., Ltd.]: A mixture of 120 parts and a mixture of 0.5 part of P3B as a 40% solution of N-methylpyrrolidone, a photo / thermal latent acid generator [sulfonium compound] , Trade name CI-2624:
Nippon Soda Co., Ltd.]: 1.0 part, acylphosphine oxide-based photopolymerization initiator having photosensitivity from ultraviolet light to visible light region [trade name, Irgacure-1800: manufactured by Ciba Geigy Co., Ltd .; 1800]: 1.0 part was mixed to obtain a one-pack putty. (Application and Curing of Primer) The same operation as in Example 1 was performed on the above one-pack putty. (Applying and curing of putty) A one-pack type putty was thinly applied (0.8 kg / m ² ) exactly as in Example 1, and
When light irradiation was carried out at a distance of 1 m for 5 minutes using, the surface was free of tack and hardened. (FRP lining) The same test as in Example 1 was performed. (Adhesion test) When a test similar to that in Example 1 was performed, the concrete was peeled off by about 5 to 10 mm by breaking the concrete base material. Adhesion is good,
It was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength.

(Example 3) (Pate composition) A mixture of 100 parts of Lipoxy RF-304X, 5 parts of Cavozil TS-720, and 100 parts of talc (trade name: talc LMR, manufactured by Fuji Talc Kogyo KK) And 0.5 part of P3B was added to N-methylpyrrolidone 40.
% Solution, MK-1: 0.2 part, CI-2855: 1.0
A putty B having exactly the same composition except that it was replaced with a part was used. (Application and Curing of Primer) The same operation as in Example 1 was performed on the above one-pack putty. (Applying and curing of putty) Next, as in Example 1, putty A
And putty B mixed at a ratio of 50 parts / 50 parts with a thin coat (0.8 kg / m ² ), and using lamp 1 and irradiating light for 5 minutes at a distance of 1 m, the surface tack is reduced. It was hardened. (FRP lining) The same test as in Example 1 was performed. (Adhesion test) When a test similar to that in Example 1 was performed, the concrete was peeled off by about 5 to 10 mm by breaking the concrete base material. Adhesion is good,
It was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength. When a test similar to that in Example 1 was performed, the concrete was peeled by about 5 to 10 mm when the concrete base material was destroyed. It was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength.

(Example 4) (Pate composition) Lipoxy RF-304X: 100 parts, Cabozir TS-720: 5 parts, talc (trade name: talc LMR, manufactured by Fuji Talc Kogyo KK), 50 parts, Heidilite HBT -320: In a mixture of 80 parts, P3B:
0.5 part of a 40% solution of N-methylpyrrolidone, bis (2
-O-chlorophenyl-4,5-diphenyl) imidazole [manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter abbreviated as BIm]:
A mixture of 1.0 parts was putty A, and P3 in putty A
B: 0.5 part of a 40% solution of N-methylpyrrolidone and BI
Putty B was of exactly the same composition except that m: 1.0 part was replaced by MK = 1: 4.0 part. (Application and curing of primer) The same operation as in Example 1 was performed. (Applying and curing of putty) Next, as in Example 1, putty A
And putty B mixed at a ratio of 50 parts / 50 parts with a thin coat (0.8 kg / m ² ), and using lamp 1 and irradiating light for 5 minutes at a distance of 1 m, the surface tack is reduced. It was hardened. (FRP lining) The same test as in Example 1 was performed. (Adhesion test) When a test similar to that in Example 1 was performed, the concrete was peeled off by about 5 to 10 mm by breaking the concrete base material. Adhesion is good,
It was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength.

(Example 5) (Putty composition) Lipoxy RF-304X: 100 parts, Cabosil TS-720: 5 parts, Heidilite HBT-
320: 160 parts, P3B: 0.5 part of a 40% solution of N-methylpyrrolidone, and BIm: 1.0 part were mixed as putty A, and P3B in putty A: 0.
5 parts of a 40% solution of N-methylpyrrolidone and BIm: 1.
0 parts: CI-2855: 2.0 parts, I-1800: 1.
Putty B was of exactly the same composition except that it was replaced with 0 parts. (Application and curing of primer) The same operation as in Example 1 was performed. (Applying and curing of putty) Next, as in Example 1, putty A
And putty B mixed at a ratio of 50 parts / 50 parts with a thin coat (0.8 kg / m ² ), and using lamp 1 and irradiating light for 5 minutes at a distance of 1 m, the surface tack is reduced. It was hardened. (FRP lining) The same test as in Example 1 was performed. (Adhesion test) When a test similar to that in Example 1 was performed, the concrete was peeled off by about 5 to 10 mm by breaking the concrete base material. Adhesion is good,
It was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength.

(Comparative Example 1) (Putty composition) As in Example 1, Lipoxy RF-304
X: 100 parts, Cavosil TS-720: 5 parts, Heidilite HBT-320: 160 parts, and a room temperature curing agent [Permec N (manufactured by NOF Corporation) /
A mixture obtained by mixing 1.2 / 0.5 parts of cobalt naphthenate was used as a room temperature-curable putty. (Application and curing of primer) The same operation as in Example 1 was performed. (Applying and Curing of Putty) Next, Example 1 and a room temperature curing type putty were thinly applied (0.8 kg / m ² ) and left at room temperature for 6 hours to cure. (FRP lining) The same test as in Example 1 was performed. (Adhesion test) When a test similar to that in Example 1 was performed, most of the destruction was caused by destruction of the concrete base material, and the concrete was peeled off by about 5 mm. However, it took a long time to cure the putty and the work efficiency was poor. Table 1 shows the adhesive strength.

[0036]

[Table 1]

(Embodiment 6) Lipoxy RF-304X: 1
00 parts, Cabosil TS-720: 5 parts, Heidilite HBT-320: 160 parts, and P3
B: 0.5 part of N-methylpyrrolidone mixed as a 40% solution, CI-2624: 1.0 part, I-180
0: 1.0 part was mixed to make a one-pack putty,
Filling into a frame of cm × 20 cm × 20 mm in thickness and irradiating the light with a lamp 1 at a distance of 1 m for 10 minutes also cured the back surface of 20 mm in thickness. A compression test according to JIS K-7208 was performed to confirm the strength of the cured putty, and it was found that the putty had sufficient strength to be used as a putty for construction and civil engineering. It was confirmed that a putty having a thickness of 20 mm could be sufficiently cured in a short time of 15 minutes. The results are shown in Table 2.

Comparative Example 2 Lipoxy RF-304X: 1
00 parts, a mixture of 5 parts of Cavozil TS-720 and 160 parts of Heidilite HBT-320, and a room temperature curing agent Permec N / cobalt naphthenate 1.2 / 0.
A mixture of 5 parts was used as a cold-curing putty, and 20 cm2
A compression test according to JIS K-7208 was carried out for a resin filled in a frame having a thickness of 0 cm and a thickness of 20 mm, left to cure at room temperature for one day, and then further cured at 120 ° C. for 2 hours. The cured product that had been left to stand for one day had a lower strength than that of Example 6 and after-cured at 120 ° C. for 2 hours. Table 2 shows the results.

Comparative Example 3 Lipoxy RF-304X: 1
00 parts, a mixture of 5 parts of CABOSIL TS-720 and 160 parts of Heidilite HBT-320, and I-
1800: 1.0 part was mixed to form a one-pack putty, and curing was attempted in the same manner as in Example 6. However, even after light irradiation for 1 hour, the back surface was not cured.

[0040]

[Table 2]

[0041]

The present invention relates to a novel putty composition for concrete construction and a method for curing the same.
(A) 100 parts by weight of a polymerizable unsaturated compound, (B) 10 to 300 parts by weight of a filler, and (C) a photocurable composition containing a polymerization initiator mainly composed of an acidic compound and a specific organic boron compound. A putty composition for concrete construction and a curing method thereof have been developed. Conventionally, putty compositions used for lining or coating on concrete or cement mortar layers of buildings and structures in the field of construction and civil engineering are usually room temperature-curing putties, and until fully cured. It takes a long time and the work efficiency is poor, and because it is necessary to prepare on-site, it is difficult to adjust the pot life and it is difficult to handle, and also it is possible to handle dangerous substances such as peroxide as a curing agent. Explosion and fire hazards were high because they were necessary. On the other hand, the putty composition of the present invention can be cured in an extremely short time by light irradiation, and can be cured by a dark reaction even in a portion where it is difficult to sufficiently irradiate light. It is a simple putty composition. Furthermore, the putty composition is an excellent novel putty composition which, when cured, has a higher adhesive strength than conventional putty compositions, is safe, and has less contamination of the working environment.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 14, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin used in the present invention includes an unsaturated polyester resin and a vinyl ester resin (hereinafter, both resins may be collectively referred to as a resin or the like).
Use at least one of them. The unsaturated polyester resin used in the present invention is a condensation product (unsaturated polyester) obtained by an esterification reaction between a polyhydric alcohol and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid).
Is dissolved in a polymerizable monomer such as styrene, and is a resin described in "Polyester Resin Handbook" Nikkan Kogyo Shimbun, published in 1988 or "Paint Glossary" edited by Coloring Material Association, published in 1993, etc. is there.
The vinyl ester resin is also called an epoxy acrylate resin, and is generally formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. It is a compound (vinyl ester) with an unsaturated bond, "Polyester Resin Handbook"
This resin is described in Nikkan Kogyo Shimbun, 1988, or “Paint Glossary”, edited by Color Materials Association, 1993. The unsaturated polyester used as a raw material of these resins and the like may be produced by a known method, and specifically, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, etc. And a saturated polybasic acid or an anhydride thereof having no polymerizable unsaturated bond and an unsaturated polybasic acid or an anhydride thereof having an active unsaturated bond such as fumaric acid, maleic anhydride, maleic acid, and itaconic acid. An acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl- 1,3-
Propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol,
It is produced by reacting a polyhydric alcohol such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A as an alcohol component.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

Examples of the saturated dicarboxylic acid used for the terminal carboxyl polyester include dicarboxylic acids having no active unsaturated group, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid and sebacic acid. Examples of the unsaturated dicarboxylic acid include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, and itaconic acid. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, -Methyl-1,
And polyhydric alcohols such as 3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A. Can be As an epoxy compound containing an α, β-unsaturated carboxylic acid ester group used for producing a vinyl ester, glycidyl methacrylate is a typical example.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

Examples of the cation "Z ⁺ " include quaternary ammonium cation, quaternary pyridinium cation, quinolinium cation, diazonium cation, tetrazonium cation, phosphonium cation, (oxo) sulfonium cation, sodium Metal cations such as potassium, lithium, magnesium, calcium, etc., (organic) compounds having a cation charge on oxygen atoms such as flavylium and pyranium salts, carbon cations such as tropinium and cyclopropylium, and halogen cations such as iodonium ion,
Arsenic, cobalt, palladium, chromium, titanium, tin,
Examples include cations of metal compounds such as antimony.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

Among these acidic compounds, (anhydride) maleic acid, fumaric acid, or a half ester thereof,
An acidic compound having a polymerizable unsaturated group such as (meth) acrylic acid and itaconic acid, or an oligomer or polymer having such a functional group is preferably used.
Further, the compound itself is not an acidic substance itself, and a compound which decomposes or reacts by the action of heating, moisture in the air, oxygen or the like to generate an acidic compound also falls under the acidic compound of the present invention. Substances that decompose by light irradiation to generate an acidic compound are also known. For example, a compound called a photocationic polymerization initiator also corresponds to the acidic compound of the present invention. Various compounds such as diazonium compounds, sulfonium compounds, iodonium compounds, and metal complex compounds are known as photocationic initiators. “Functional Materials”, October 1985, p. 5, “Applications and Markets of UV / EB Curing Technology” ", Page 78, published by CMC Inc., 1989. Among these compounds to be referred to as latent acidic compounds, compounds that generate an acid by light or heat are desirable in view of availability, economy, stability in a composition, operability, and the like. Compounds that generate an acid by heat are more preferable, and organic sulfonium compounds that generate an acid by being decomposed by heating are particularly preferable.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

A known bis (2,6-dimethoxybenzoyl)-having photosensitivity from ultraviolet light to visible light region.
2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -methylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide An acylphosphine compound such as For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 117)
3, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba-Geigy) 75% /
Trade name “IRGACURE 170” mixed at a rate of 25%
0 (manufactured by Ciba-Geigy Corporation), 1-hydroxy-cyclohexyl-phenyl ketone (trade name: "Irgacure 1")
84 "(manufactured by Ciba-Geigy) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba-Geigy).
Trade name “Irgacure 1800” (manufactured by Ciba Geigy) mixed at a ratio of 5% / 25%, 50% / 50%
"IRGACURE 1850" mixed in the ratio of
(Manufactured by Ciba Geigy Corporation), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name “Irgacure 819”), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Lucirin TPO BASF) 2)
-Hydroxy-2-methyl-1-phenylpropane-1
-One (trade name: Darocur 1173, manufactured by Ciba-Geigy Corporation) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Luciri)
n TPO BASF Co., Ltd.) in a ratio of 50% / 50%, such as “Darocur4265”. 380 nm to 78 as a visible light polymerization initiator
Any photopolymerization initiator having photosensitivity in the wavelength region of 0 nm may be used, and these may be used in combination.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

The amount of the polymerization initiator obtained by combining the organic boron compound and the (latent) acidic compound and, if necessary, the visible light polymerization initiator, or the combination of the hexaarylbiimidazole is determined by the type of the resin, Although the optimum value varies depending on the amount, thickness, etc., generally 0.01 to 20 parts by weight, preferably 0.05 to
15 parts by weight. The amount of the polymerization initiator composition used is 0.0
If the amount is less than 1 part by weight, the polymerization tends to be insufficient, and
If the amount exceeds the weight part, it is economically disadvantageous and the physical properties of the cured product are deteriorated. When the resin or the like contains an acidic compound in advance, maleic acid (anhydride) contained in the unsaturated polyester resin or the vinyl ester resin,
Fumaric acid or their half esters, (meth)
It may be acrylic acid, itaconic acid, an oligomer or polymer having a carboxyl group of the carboxylic acid at the terminal, or may be a form in which an arbitrary acidic compound is added to a resin or the like. In this case, the acid value of the unsaturated polyester resin or vinyl ester resin is 0.1
-100 mgKOH / g, preferably 5-50 mgKO
H / g.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

The composition ratio of the organic boron compound to the (latent) acidic compound in the polymerization initiator is 0.1 / 5 to 5 /
0.1, preferably 0.5 / 5 to 5 / 0.5. If the ratio of the organoboron compound to the (latent) acidic compound is too small, the curing is insufficient, and if the ratio of the organoboron compound and / or the (latent) acidic compound is too large, the economical efficiency is reduced. In addition to this, the physical properties of the cured product are reduced.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

In the present invention, a silane coupling agent may be added, if necessary, to improve the adhesion on the wet concrete surface. As a silane coupling agent, if necessary, use a moisture absorbent such as molecular sieve,
There is a method in which 0.1 to 2 to 0 parts by weight of 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, etc. is added to 100 parts by weight of the resin. . A detailed description is given in JP-A-6-271373.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

In the putty composition for concrete and the method of curing the same according to the present invention, a resin composition containing a polymerization initiator by combining an organic boron compound with an acidic compound and, if necessary, a visible light polymerization initiator. Has a long pot life, is safe with no problem of pot life, and if light is applied when it is desired to cure, the part that transmits visible light cures quickly, and the part that does not easily transmit light also contains organic boron compounds and acidic compounds. Curing progresses by the reaction described above, and furthermore, by the action of gentle heat from the light source, the portion where visible light is difficult to transmit can be completely cured, so that trouble-free and safe workability can be improved. As a result, the molded body can be cured by solving the problem of deterioration of the working environment and the problem of the pot life due to the volatilization of the reactive monomer, and it is possible to cure, and it is economical, and the light used for polymerization is safe for humans. A light source that generates both visible light and heat is sufficient. Also, since the putty composition can be a one-pack type or a safe two-pack mixing type that can be mixed one-on-one, workability can be improved safely without any trouble at the work site.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

[0029]

The present invention will be described in detail with reference to the following examples and comparative examples. In each example, "parts" and "%" are based on weight. (Example 1) (Pate composition) Vinyl ester resin [trade name: Lipoxy RF-304X: manufactured by Showa Polymer Co., Ltd.]: 100 parts, thixotropic fine-particle silica [trade name: Cavogil TS-720: Cabot, USA] (stock)
5 parts, aluminum hydroxide powder [trade name: Hijilite HBT-320, manufactured by Showa Denko KK]: 130 parts
Boron compound: tetra-n-butylammonium / triphenyl-n-butylborate [manufactured by Showa Denko KK: hereinafter abbreviated as P3B]: 0.5 part of N-methylpyrrolidone 4
The mixture obtained as a 0% solution was referred to as putty A, and a 40% solution of P3B: 0.5 part of N-methylpyrrolidone in putty A was mixed with a maleic acid type oligomer [trade name MK-
1, manufactured by Showa Polymer Co., Ltd.]: Putty B having exactly the same composition except that it was replaced with 2.0 parts. (Conditions for applying and curing the primer) A room temperature-curable primer [trade name, CP-819B, manufactured by Showa Polymer Co., Ltd.] and methyl ethyl ketone peroxide [trade name Permec N, manufactured by NOF Corporation]: 1.2 parts 30cm x 30c
mx 6cm concrete sidewalk board upper surface (30cm x 3
0 cm) with a brush (0.1 kg / m ² ) and cured and dried for half a day.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

(Applying and curing of putty) Next, for the purpose of non-land repair, a putty composition in which putty A and putty B were mixed at a ratio of 50 parts / 50 parts was thinly applied (0.8 kg / m ² ). hand,
2K which is a light source including a wavelength range of 380 to 1200 nm
W metal halide lamp [trade name: Dynabeam 2, manufactured by Toshiba Lighting & Technology Corp .; When light irradiation was performed for 10 minutes at a distance of 1 m using the above method, the surface became tack-free and cured. (FRP lining) Next, 2 pl of carbon fiber sheet (trade name: Tow sheet, manufactured by Tonen Corp.)
In y, permec N [produced by NOF Corporation / cobalt naphthenate (cobalt 6%) = 1.
A vinyl ester resin (trade name: Lipoxy R-804, manufactured by Showa Polymer Co., Ltd.) to which 5 parts / 0.5 part was added was impregnated so as to have a carbon content of 60 vol%, and was laminated on the putty cured surface. Allowed to cure. (Adhesion test) ADHESION T
The adhesive strength and the state of destruction were examined at an adhesive area of 4.9 cm ² using an ESTER elcometer, and the concrete was peeled off by about 5 mm when the concrete base material was broken. The adhesion was good, and it was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength
It was shown to.

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

Example 2 (Pate composition) Lipoxy RF-
304X: 100 parts by weight of thixotropic agent fine silica powder [trade name: Egilel # 200, manufactured by Nippon Aerosil Co., Ltd.]: 5
Parts, calcium carbonate (trade name: Softon 1200, manufactured by Bihoku Powder Chemical Industry Co., Ltd.): A mixture of 120 parts and P3
B: A mixture of 0.5 part as a 40% solution of N-methylpyrrolidone, a photo / thermal latent acid generator [sulfonium compound, trade name CI-2624: manufactured by Nippon Soda Co., Ltd.]:
1.0 part, acylphosphine oxide-based photopolymerization initiator having photosensitivity from ultraviolet light to visible light region [trade name, Irgacure-1800: manufactured by Ciba Geigy Co., Ltd .;
-1800]: 1.0 part was mixed to obtain a one-pack putty. (Application and curing of primer) The same operation as in Example 1 was performed. (Putty application and curing) Example 1
Just apply one-pack putty thinly (0.8kg /
m ² ), and when light irradiation was performed for 5 minutes at a distance of 1 m using the lamp 1, the surface was tack free and cured. (FR
P lining) The same test as in Example 1 was performed. (Adhesion test) When the same test as in Example 1 was performed, the destruction state was about 5 to 1 due to the destruction of the concrete base material.
Peeled about 0 mm. The adhesion was good, and it was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength.

[Procedure amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0032

[Correction method] Change

[Correction contents]

(Example 3) (Pate composition) Lipoxy RF-
304X: 100 parts, Cavozile TS-720: 5
Parts, 100 parts of talc (trade name: talc LMR, manufactured by Fuji Talc Kogyo KK), and P3B: 0.5
A part of the mixture was prepared as a putty A by mixing as a 40% solution of N-methylpyrrolidone. P3B in the putty A: 0.5 part of a solution of N-methylpyrrolidone in 0.5 part of MK-1: 0.2 part, CI-28
55: Putty B having exactly the same composition except that 1.0 part was replaced. (Application and curing of primer)
The same operation as in Example 1 was performed. (Applying and curing of putty) Next, as in Example 1, putty in which putty A and putty B were mixed at a ratio of 50 parts / 50 parts was thinly applied (0.
8 kg / m ² ), and light irradiation was performed using the lamp 1 at a distance of 1 m for 5 minutes. (FRP lining) The same test as in Example 1 was performed. (Adhesion test) When a test similar to that in Example 1 was performed, the concrete was peeled off by about 5 to 10 mm by breaking the concrete base material. The adhesion was good, and it was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength.

[Procedure amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

(Example 4) (Pate composition) Lipoxy RF-
304X: 100 parts, Cavozile TS-720: 5
Part, talc (trade name: Talc LMR, manufactured by Fuji Talc Kogyo KK) 50 parts, Heidilite HBT-320: 80
Of P3B: 0.5 part of a N-methylpyrrolidone 40% solution, bis (2-o-chlorophenyl-
4,5-diphenyl) imidazole [manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter abbreviated as BIm]: A mixture of 1.0 part was used as putty A, and P3B in putty A: 0.5 part of N-methyl Pyrrolidone 40% solution and BIm: 1.0 part by MK-
Putty B was of exactly the same composition except that it was replaced with 1: 4.0 parts. (Application and curing of primer) The same operation as in Example 1 was performed. (Applying and curing of putty) Next, putty A and putty B were added in the same manner as in Example 1.
0 parts / 50 parts of putty mixed thinly (0.8 parts)
kg / m ² ) and use lamp 1 at a distance of 1 m
When light irradiation was performed for a minute, the surface became tack-free and cured.
(FRP lining) The same test as in Example 1 was performed.
(Adhesion test) When a test similar to that in Example 1 was performed, the concrete was peeled off by about 5 to 10 mm by breaking the concrete base material. Adhesion is good,
It was confirmed that the performance as putty was sufficiently satisfied. Table 1 shows the adhesive strength.

[Procedure amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

[0036]

[Table 1] C: Concrete base material destruction

[Procedure amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction contents]

Comparative Example 2 Lipoxy RF-304X: 1
00 parts, a mixture of 5 parts of Cavozil TS-720 and 160 parts of Heidilite HBT-320, and a room temperature curing agent Permec N / cobalt naphthenate 1.2 / 0.
A mixture of 5 parts was used as a room temperature curing type putty, and 20 cm ×
A compression test by JIS K-7208 was carried out on a resin cured in a 20 cm × 20 mm thick frame by leaving it at room temperature for 1 day and then after-cured at 120 ° C. for 2 hours. The cured product that had been left to stand for one day had a lower strength than that of Example 6 and after-cured at 120 ° C. for 2 hours. Table 2 shows the results.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shuichi Sugita 1-1-1 Onodai, Midori-ku, Chiba-shi, Chiba Prefecture Showa Denko KK Research Institute (72) Inventor Hirotoshi Kamata 1-1, Onodai, Midori-ku, Chiba-shi, Chiba -1 Showa Denko KK

Claims (12)

[Claims] (A) a polymerizable unsaturated compound: 100 parts by weight; (B) a filler: 10 to 300 parts by weight; (C) an acidic compound and an organic boron compound represented by the general formula (1). A putty composition for a concrete structure, comprising a polymerization initiator. Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, A substituted aryl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a cation) (A) a polymerizable unsaturated compound: 100 parts by weight; (B) a filler: 10 to 300 parts by weight; (C) an acidic compound and an organic boron compound represented by the general formula (1). A putty composition for a concrete structure, comprising: a polymerization initiator; and (D) a visible light polymerization initiator. 3. The putty composition according to claim 2, wherein the visible light polymerization initiator is an acylphosphine oxide compound. (A) a polymerizable unsaturated compound: 100 parts by weight; (B) a filler: 10 to 300 parts by weight; (C) an acidic compound; an organic boron compound represented by the general formula (1); A putty composition for a concrete structure, comprising a polymerization initiator comprising a hexaarylbiimidazole represented by the formula (2). Embedded image (In the formula, L ¹ , L ² and L ³ each independently represent an aryl group or a substituted aryl group.) (A) a polymerizable unsaturated compound: 100 parts by weight; (B) a filler: 10 to 300 parts by weight; (C) an acidic compound; an organic boron compound represented by the general formula (1); A putty composition for concrete construction, comprising: a polymerization initiator comprising a hexaarylbiimidazole represented by the formula (2); and (D) a visible light polymerization initiator. 6. The putty composition according to claim 1, wherein the polymerizable unsaturated compound is an unsaturated polyester resin, a vinyl ester resin and / or an acrylic resin. 7. The putty composition according to claim 1, wherein the filler is an inorganic and / or organic filler. 8. The acidic compound is at least one of a polymerizable unsaturated compound such as (anhydride) maleic acid, fumaric acid or a half ester thereof, (meth) acrylic acid, and itaconic acid, or an oligomer or a polymer containing the acidic compound. The putty composition according to any one of claims 1 to 7, which is selected from one kind. 9. The acidic compound according to claim 1, wherein the acidic compound is a latent acid generator that generates an acid by light irradiation and / or heating.
8. The putty composition according to any one of 8 above. 10. The putty composition according to claim 9, wherein the latent acid generator is an organic sulfonium compound. 11. A method for curing a putty composition, comprising curing the putty composition according to claim 1 by light irradiation and / or heating. 12. The light source for light irradiation is a light source that emits light having a wavelength in the visible light and / or near-infrared light region.
A method for curing the putty composition according to claim 1.