JP6567599B2 - Curable resin composition, concrete coating composition and lining material - Google Patents

Description

  The present invention is particularly excellent in low odor, adhesiveness, chemical resistance, surface air curability, heat resistance, wear resistance, high reactivity, durability, lining material for surface coating of concrete in sewerage treatment facilities, A curable resin composition suitable for forming a repair lining material for the inner surface of a human hole and the like, and a repair lining material for a concrete facility of a food factory, a pharmaceutical factory, an electronic material related factory, and a concrete coating containing the curable resin composition The present invention relates to a composition and a lining material.

The gas phase part of the concrete structure of the sewage treatment facility is sulphated by hydrogen sulfide by sulfur-oxidizing bacteria, and the surface is weakened by long-term use, affecting the structural strength of the facility.
The repair method for an aged sewerage treatment facility is usually applied by applying a cross-section repair material to the deteriorated layer thickness of the wall surface of an existing deteriorated concrete structure, applying a primer after curing, and then applying a substrate conditioner for the purpose of unevenness adjustment. A method of applying a coating type resin lining material is used. In addition, in the case of a new structure, a method is used in which a primer is applied to a concrete base, and then an anticorrosion coating resin lining material is applied after applying a base material adjusting material for the purpose of adjusting unevenness.

  As a curable resin composition used for the coating type resin lining material as described above, an unsaturated polyester resin composition has been conventionally used, and recently, an unsaturated monobasic acid, particularly acrylic acid, is used as an epoxy resin. Or the resin composition (generally vinyl ester resin composition) containing the epoxy (meth) acrylate obtained by making methacrylic acid react is also used.

Of known unsaturated polyester resin compositions and vinyl ester resin compositions used for coating lining materials, styrene monomers are generally used as the copolymerizable monomer. However, this mixture of ester and styrene has a characteristic odor, and this odor diffuses into the environment around the construction and causes a problem. Therefore, a method of adsorbing the generated styrene with an activated carbon adsorption device has been introduced. Styrene is subject to the PRTR system (Chemical Emission Control Management Promotion Act), a type 1 designated chemical substance, and a system for disclosing released and transferred amounts. In addition, styrene is designated as a specified chemical substance on November 1, 2014 (Ministry of Health, Labor and Welfare), and its management is required, and regulations on the styrene concentration in styrene-containing unsaturated polyester resins and vinyl ester resins become stricter. The countermeasures are urgently needed.

  A composition comprising a mixture of a so-called epoxy acrylate (or epoxy methacrylate) and a monomer copolymerizable with this ester obtained by reacting an epoxy resin with an unsaturated monobasic acid, particularly acrylic acid or methacrylic acid, is known. is there. This composition has heretofore been used, for example, as a matrix for fiber-reinforced plastics.

  About the technique of a low odor resin composition, the technique concerning low odor is disclosed by the following patent documents 1-10. Moreover, the lining material using the photopolymerizable resin composition that is added with a photopolymerization initiator to the curable resin composition and cured by ultraviolet irradiation is disclosed in, for example, the following Patent Documents 11 to 16, etc. Patent Document 15 (Japanese Patent Laid-Open No. 2003-33970) describes a photocurable material containing an unsaturated polyester and / or vinyl ester resin (epoxy resin) and a bisacylphosphine oxide compound.

  However, such a resin composition is still not sufficient in terms of low odor, water resistance, chemical resistance, durability, adhesion, and air drying performance.

  Furthermore, about the technique of an aqueous resin composition, the technique concerning an aqueous system is disclosed by the following patent documents 17-25. In any case, an active hydrogen-containing compound, a polyisocyanate compound, hydraulic cement, water, and a cement water reducing agent are basic constituent elements.

However, none of the materials has sufficient properties such as strength, waterproofness, and adhesiveness of the cured product and curing properties.

Japanese Patent Laid-Open No. 6-211952 Japanese Patent Laid-Open No. 11-12448 Japanese Patent Laid-Open No. 9-15337 Japanese Patent Laid-Open No. 11-12448 Japanese Patent Laid-Open No. 10-231453 JP-A-11-255847 JP 2001-240632 A JP 2002-60282 A Japanese Patent Laid-Open No. 11-106452 Japanese Patent Laid-Open No. 50-59497 Japanese Patent Laid-Open No. 11-199639 Japanese Patent Publication No. 60-8047 JP-A-1-92214 JP-A-2-188227 JP-A-11-210981 JP 2003-33970 A JP 2000-72507 A JP-A-8-169740 JP-A-8-169744 JP-A-2005-47719 JP 2002-179454 A JP 2000-302514 A JP 2009-29682 A JP 2006-240919 A JP 11-79820 A Japanese Patent No. 3897657 JP 2004-095991 A JP 2006-009461 A JP-A-9-169898 JP 2014-095002 A

  The present invention aims to provide a non-styrene type vinyl ester resin, and in particular, the physical properties of cast and laminated plates are the same level as that of the styrene type vinyl ester resin. An object of the present invention is to provide a non-styrene type vinyl ester resin that maintains an initial value of adhesion strength even after long-term immersion and has a weight change rate after immersion in warm water equivalent to that of a cured styrene type vinyl ester resin. Furthermore, the present invention can arbitrarily adjust the mechanical strength, low odor, adhesiveness, chemical resistance, surface air curing, crack resistance, wear resistance, high reactivity, durability, photocurability. An object of the present invention is to provide a non-styrenic vinyl ester resin-based curable resin having a good quality. Furthermore, this invention aims at providing the concrete coating composition and lining material which have said characteristic.

  In order to solve the above problems, the present inventors have found that the above problems can be solved by a curable resin composition containing the following components (A) to (E).

  That is, the present invention is as follows.

  1) (A) A urethane (meth) acrylate having at least two (meth) acryloyl groups at the molecular end, (B) a reaction product of an aromatic epoxy resin and (meth) acrylic acid, and a number average molecular weight Is an epoxy (meth) acrylate having an acid value of 10 KOHmg / g or less, (C) an ethoxylated bisphenol di (meth) acrylate having 2 to 10 moles of ethylene oxide added, and (D) A monofunctional (meth) acrylate monomer having a group including a cyclic hydrocarbon group having only one carbon-carbon double bond or one nitrogen atom in the ring as an alcohol residue having a molecular weight of 300 or less, and ( (E) (Meth) acrylate monomers 1 to 1 having a phenyl group with respect to 100 parts by mass in total of A), (B), (C) and (D) Parts by weight of a curable resin composition comprising a. If this curable resin composition is used, the use of a copolymerizable monomer (such as styrene) that has a specific odor and is restricted in use can be reduced to zero, or the amount used can be reduced.

  2) A preferable composition of the above components (A) to (D) is, for example, (A) urethane (meth) acrylate with respect to 100 parts by mass in total of components (A), (B), (C) and (D). 10-50 parts by weight, (B) 5-50 parts by weight of epoxy (meth) acrylate, (C) 3-30 parts by weight of ethoxylated bisphenol di (meth) acrylate, (D) monofunctional (meth) acrylate monomer 15 1 to 10 parts by mass of (E) phenyl group-containing (meth) acrylate monomer with respect to a total of 100 parts by mass of (A), (B), (C) and (D). The weight ratio (A) / (B) of (A) urethane (meth) acrylate and (B) epoxy (meth) acrylate is 70/30 ≦ (A) / (B) <95/5, (B) of epoxy (meth) acrylate The average molecular weight is in the range of 500 to 1100, more preferably in the range of 500 to 1000, and (C) ethoxylated bisphenol A di (meth) acrylate is a bifunctional (meth) acrylate monomer ethoxylated bisphenol A di (meth) acrylate It is characterized by being. When a curable resin composition having this composition is cured, a soft cured product is obtained.

  3) Other preferable compositions of the above components (A) to (D) are, for example, (A) urethane (meta) with respect to a total of 100 parts by mass of components (A), (B), (C) and (D). ) 10-50 parts by mass of acrylate, (B) 5-50 parts by mass of epoxy (meth) acrylate, (C) 3-30 parts by mass of ethoxylated bisphenol A di (meth) acrylate, and (D) monofunctional (meta) ) 15-15 parts by mass of an acrylate monomer, and (E) a (meth) acrylate monomer having a phenyl group with respect to a total of 100 parts by mass of (A), (B), (C) and (D). 1 to 10 parts by mass, and the weight ratio (A) / (B) of (A) urethane (meth) acrylate and (B) epoxy (meth) acrylate is 5/95 ≦ (A) / (B) <70/30 and (B) epoxy ( The number average molecular weight of the acrylate is in the range of 500 to 1100, more preferably in the range of 500 to 1000, and (C) ethoxylated bisphenol A di (meth) acrylate is a difunctional (meth) acrylate monomer ethoxylated bisphenol A It is di (meth) acrylate. When the curable resin composition having this composition is cured, a hard cured product is obtained.

  4) The (A) urethane (meth) acrylate (urethane (meth) acrylate oligomer) is a polyalkylene glycol having a weight average molecular weight of 400 to 700, a polyisocyanate, and a (meth) acrylate monomer having at least one hydroxyl group. can get.

  5) Furthermore, this invention also provides the lining material containing the curable resin composition in any one of the said.

  6) It is good also as a lining material by adding 1-30 mass parts of thickeners which consist of a thermoplastic resin powder with respect to 100 mass parts of said curable resin compositions.

  7) It is good also as a lining material by adding 0.5-2.5 mass parts of photoinitiators with respect to 100 mass parts of said curable resin compositions.

  8) It is good also as a lining material by adding 5-50 mass parts of scale-like inorganic fillers with respect to 100 mass parts of the said curable resin composition.

  9) Further, an organic peroxide may be added to form a lining material.

10) Further, a hydraulic cement and a cement water reducing agent may be added to form a lining material. In this case, the mixture has the blending ratio of 2) and contains the organic peroxide of 9). Most preferred is that the component B) is a bifunctional (meth) acrylate monomer ethoxylated bisphenol A di (meth) acrylate.
11) When using the said hydraulic cement and a cement water reducing agent, the water required for the hydration hardening of (F) hydraulic cement is contained in a lining material in the case of use.

  12) 100-600 parts by mass of a fine particle or powdery inert inorganic material may be added to 100 parts by mass of any of the above curable resin compositions to form a concrete coating composition. The average particle size of the material is preferably in the range of 10 mm to 0.02 mm.

According to the present invention, even without using a highly regulated copolymerizable monomer such as styrene, the disadvantages of the prior art are eliminated, low odor, water resistance, crack resistance, chemical resistance, durability, It is possible to provide a curable resin composition having excellent adhesion and air drying properties. The curable resin composition of the present invention can be used for various applications such as a concrete coating composition and a lining material having the above-mentioned properties, and has no styrene odor before and after curing, so there is no environmental pollution. Since the resin composition of the present invention can change the properties of the cured product from hard to soft by changing the mass ratio of the components (A) and (B), it can meet various physical property requirements.

  Hereinafter, components (A), (B), (C), (D) and (E) used in the curable resin composition of the present invention and other components which can be optionally added will be described in detail. The present invention is not limited to this.

<Component (A)>
In the present invention, the component (A) of the curable resin composition is one of the essential components of the curable resin composition.

  The urethane (meth) acrylate as the component (A) has a compound having one or more hydroxyl groups and one or more copolymerizable unsaturated groups in one molecule and two or more hydroxyl groups in one molecule. A polymer produced from a glycol and / or polyol and a compound having two or more isocyanates in one molecule by a known method, for example, the method described in JP-B-55-30527 or JP-B-60-26132 A polymer having a urethane bond in the chain and an acryloyl group or a methacryloyl group at the polymer terminal.

  For example, the component (A) is preferably a urethane (meth) acrylate obtained by reacting and synthesizing polyalkylene glycol, polyisocyanate, and a (meth) acrylate monomer having one or more hydroxyl groups in one molecule.

  Even more preferred is a polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit of the alkylene group of the polyalkylene glycol, and more preferred is polypropylene glycol. By using these polyalkylene glycols, (A) urethane (meth) acrylate having at least two (meth) acryloyl groups at the molecular terminals can be synthesized. By using this (A) urethane (meth) acrylate and (B) epoxy (meth) acrylate described later, a cured product having characteristics such as low odor, durability, crack follow-up resistance, and impact resistance can be obtained. can get. Moreover, the weight ratio of (A) urethane (meth) acrylate and (B) epoxy (meth) acrylate can be changed, and the hardness of hardened | cured material can be adjusted from soft to hard. For example, the component (A) is used in a larger amount than the component (B), more specifically, by setting the weight ratio (A) / (B) of these components to 70/30 or more and less than 95/5, A resin composition for physical use is obtained. On the contrary, the component (B) is used in a larger amount than the component (A), more specifically, the weight ratio (A) / (B) of these components is 5/95 or more and less than 70/30. Thus, a resin composition for a hard cured product is obtained. As will be described later, it is more preferable to control the molecular weight of the raw material (polyol) of (A) urethane (meth) acrylate to adjust the physical properties of the cured product.

  The urethane methacrylate (A) has a urethane bond in the polymer chain, and has, for example, an acryloyl group or a methacryloyl group, that is, a (meth) acryloyl group at the polymer terminal. Such a urethane (meth) acrylate includes a compound having one or more hydroxyl groups (hydroxyl groups) and one or more (meth) acryloyl groups (copolymerizable unsaturated groups) in one molecule, and two or more in one molecule. Of a hydroxyl group-containing compound and an aromatic and / or aliphatic polyisocyanate compound, for example, Japanese Patent Publication No. 55-30527, Japanese Patent Publication No. 55-8013, Japanese Patent Publication No. 54-21879, Japanese Patent Publication No. It can be produced by a method as described in JP-A-60-326132 and JP-B-60-26133.

In the compound having one or more hydroxyl groups and one or more copolymerizable unsaturated groups in one molecule,
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyhydropropyl (meth) acrylate, trimethylolpropan (meth) acrylate, dipyropyrene glycol mono (meth) acrylate Etc. can be used.

Further, the compound having two or more hydroxyl groups in one molecule is, for example, glycol and / or polyol, and more specifically,
-Neopentyl glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, glycols such as hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, adipic acid, (anhydrous) phthalic acid, isophthalic acid , Saturated polyester polyol having a molecular weight of 1000 to 2000 obtained from a dehydration condensation reaction with a polybasic acid such as terephthalic acid or trimellitic acid,
-Polyethylene glycol having a molecular weight of 300 to 2000 obtained by a ring-opening reaction of ethylene oxide or propylene oxide,
-Polypropylenes, or
-Polycaprolactone obtained by ring-opening reaction of caprolactone, etc., and these can be used alone or in combination of two or more. When the molecular weight of the glycol and / or polyol component is within the above range, the viscosity of the resulting resin composition is good, and the workability of the step of impregnating the reinforcing resin with the liquid resin composition and the impregnating resin composition is improved. Is also preferable.

  In addition to the weight ratio (A) / (B) described above, more preferably, the physical properties of the cured product are controlled by controlling the molecular weight of glycol and / or polyol. For example, if the polyol (glycol) has a high molecular weight, the softness (EL) of the cured product increases, but the tensile strength (TS), which is a structural property governing factor, may decrease, so the weight of the polyol (glycol) The average molecular weight is preferably 700 or less. Most desirably, a polyol and / or glycol having a weight average molecular weight of 400 to 700 is used, and the weight ratio (A) / (B) is controlled to control hard and soft. In addition, when using 2 or more types of polyol (glycol), the weight average molecular weight of the whole polyol (glycol) should just be 400-700.

  As the polyisocyanate, that is, a compound having two or more isocyanate groups in one molecule, aromatic and / or aliphatic polyisocyanate compounds are used. For example, tolylene isocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane. Diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate and the like can be mentioned, and these can be used alone or in admixture of two or more.

  The polypropylene glycol used preferably has a weight average molecular weight of 200 to 3000, more preferably 300 to 2000, and most preferably 400 to 700. When the molecular weight is smaller than this range, the flexibility (elongation rate) of the cured product is reduced and the resin viscosity is significantly increased. On the other hand, if the molecular weight is larger than this range, the flexibility is increased, but the strength may be lowered. Examples of polyalkylene glycols other than polypropylene glycol include polyether polyols such as polyethylene glycol, polytetramethylene ether glycol (polytetrahydrofuran), and polyols obtained by adding alkylene oxide to bisphenol A or bisphenol F.

Other polyols can be used in combination with the polyalkylene glycol as long as various physical properties are not impaired. Typical examples of the polyol that can be used include polyester polyol, polycarbonate polyol, polybutadiene polyol, and hydrogenated polybutadiene polyol. Polyester polyol is a condensation polymer of dibasic acids and polyhydric alcohols,
Or it is a ring-opening polymer of a cyclic ester compound like polycaprolactone. Examples of dibasic acids used here include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, succinic acid, and malonic acid. , Glutaric acid, adipic acid, sebacic acid, 1,12 dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, or dialkyl esters thereof.

  More preferably, the raw material of the component (A) is reacted until the NCO group content is 5 mol% or less, more preferably 1 mol% or less, and most preferably the NCO group disappears (substantially 0%) (A). Ingredients.

  In this invention, the usage-amount of urethane (meth) acrylate (A) is 10-50 mass% with respect to 100 mass% of total amounts of component (A), (B), (C), and (D), Preferably It is the range of 20-50 mass%. When the amount of (A) used is too small, the cured product of the resulting curable resin composition has a low resistance to crack follow-up, and when the amount of (A) is too large, the cured product is whitened by long-time immersion in warm water. Is likely to occur.

<Component (B)>
In the present invention, epoxy (meth) acrylate (B) which is one of the essential components of the curable resin composition is an aromatic epoxy (meth) acrylate obtained from an aromatic epoxy compound and (meth) acrylic acid. In the present invention, those having a number average molecular weight in the range of 500 to 1100, more preferably having a number average molecular weight of 500 to 1000 and an acid value of 10 KOHmg / g or less are used.

  The aromatic epoxy resin used as a raw material for the component (B) is an epoxy resin having an aromatic in the molecule, such as a phenol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, Examples thereof include bisphenol S-type epoxy resins, alkylphenol-type epoxy resins, resorcin-type epoxy resins, N-glycidylamine-type epoxy resins, and brominated bisphenol A-type epoxy resins. These epoxy resins may be used alone or in combination of two or more. Of these, bisphenol A type epoxy resins are more preferred in that they provide balanced properties to the concrete coating curable resin composition and the lining material cured product.

  The unsaturated monobasic acids to be reacted with the epoxy resin are acrylic acid and methacrylic acid, but other unsaturated monobasic acids such as crotonic acid, sorbitan acid, cinnamic acid, acrylic acid dimer, monomethyl acrylate, monomethyl fumarate, mono A small amount of cyclohexyl fumarate or sorbic acid can be used in combination. These acids can be used alone or in combination of two or more.

  The aromatic epoxy (meth) acrylate (B) used in the curable resin composition of the present invention is obtained from a normal reaction between the aromatic epoxy resin and (meth) acrylic acid, The reaction ratio of (meth) acrylic acid is usually in the range of 0.9 to 1.1: 1.1 to 0.9 in terms of molar ratio. The reaction at this time is usually carried out at 80 to 130 ° C., and the reaction catalyst is a tertiary amine such as triethylamine or dimethylaniline, a quaternary ammonium salt such as trimethylbenzylammonium chloride or pyridinium chloride, lithium hydroxide, lithium chloride or the like. Inorganic salts are used. A polymerization inhibitor may be used as necessary.

As polymerization inhibitors, hydroquinones such as hydroquinone and methylhydroquinone,
Benzoquinones such as benzoquinone and methyl-p-benzoquinone, catechols such as t-ptylcatechol, phenols such as 2,6-di-t-butyl-t-methylphenol and 4-methoxyphenol, phenothiazine, etc. . The addition amount of the esterification catalyst can be used in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the aromatic epoxy resin and (meth) acrylic acid. Preferably it can be used in the range of 0.05 to 5 parts by mass. If the amount is less than 0.01 parts by mass, the esterification reaction becomes extremely slow. If the amount exceeds 10 parts by mass, the esterification reaction becomes extremely fast, and temperature control becomes difficult due to rapid heat generation, which is not preferable.

  In this invention, the usage-amount of aromatic epoxy (meth) acrylate (B) is 5-50 mass% with respect to 100% of the total amount of component (A), (B), (C) and (D). It is a range. That is, when the component (B) is less than 5 parts by mass with respect to the total of 100 parts by mass of the components (A), (B), (C), and (D), the cured product of the resulting curable resin composition has a long time. A whitening phenomenon occurs by immersion in hot water, and if it exceeds 40 parts by mass, a shrinkage crack is likely to occur during curing.

  Further, when the number average molecular weight of the aromatic epoxy (meth) acrylate (B) is less than 500, there is a disadvantage that the terminal acryloyl group concentration increases and the water absorption increases, and when the terminal group and ester bond density increases, the alkali resistance is increased. On the other hand, when the number average molecular weight exceeds 1100, the viscosity of the curable resin composition during synthesis and the curable resin composition is increased, workability is lowered, and solvent resistance is also inferior.

  In order to balance the above performance, 0.3 to 0.7 mol% of a liquid type epoxy resin having a molecular weight of 500 or less and 0 to a solid type epoxy resin having a molecular weight of 900 or more are usually added to 1 mol of an aromatic epoxy resin. It is also possible to obtain an aromatic epoxy (meth) acrylate from a reaction product of a resin having a composition ratio in the range of 7 to 0.3 mol% and (meth) acrylic acid, and use this as the component (B). .

  In addition, when the acid value exceeds 10 KOH mg / g, the monomer of unsaturated monobasic acrylic acid or methacrylic acid having an irritating odor remains in the aromatic epoxy (meth) acrylate, which is not preferable.

  In addition, molecular weight is a polystyrene conversion value here, and an acid value is the value measured by JISK25012003.

<Component (C)>
The component (C) of the resin composition used in the present invention is ethoxylated bisphenol di (meth) acrylate having 2 to 10 moles of alkylene oxide added, and bisphenol (preferably bisphenol A and / or bisphenol F) is alkylene oxide. An ester compound of a dihydric alcohol to which is added and (meth) acrylic acid is raised. As the raw material bisphenol, one or both of bisphenol A and bisphenol F, particularly bisphenol A is preferable, and the alkylene oxide is more preferably ethylene oxide in consideration of reactivity.

The ethylene oxide of the ethoxylated bisphenol di (meth) acrylate of component (C) has a reduced crosslinking density when the number of added moles is 10 or more, the reactivity of the curable resin composition is lowered, the water resistance of the cured product, In addition to increasing the weight change rate of normal temperature water and hot water immersion, as a chemical resistance, an electron beam microanalyzer (dipping a cured product for 120 days in a 10% sulfuric acid aqueous solution specified in the guidelines of the Japan Sewerage Corporation, for example) EPMA) is a test method for predicting the durability life of lining materials by the penetration depth of sulfur in sulfuric acid, because the penetration depth increases, the affinity with fiber reinforcement, and the adhesive strength decrease. Use is unsuitable. On the other hand, when the number of moles of ethylene oxide added is 2 or less, the viscosity of the resin composition is increased, which makes it difficult to work.

  Content of this component (C) is the range of 3-30 mass parts with respect to a total of 100 parts of a component (A), (B), (C), and (D). That is, the surface of the cured product of the curable resin composition obtained by less than 3% by mass with respect to the total of 100% by mass of the components (A), (B), (C) and (D) is immersed in room temperature water and warm water. A whitening phenomenon occurs, and if it is 30% by mass or more, swelling occurs in the cured product of the curable resin composition when immersed in water or warm water, which is not preferable. Although the manufacturing method of ethoxylated bisphenol di (meth) acrylate (C) is not specifically limited, For example, it can manufacture by the well-known method of Unexamined-Japanese-Patent No. 7-268079. More specifically, first, diglycidyl ether of ethylene oxide adduct of bisphenol A is subjected to ether reaction with nucleated polyol obtained by adding ethylene oxide to bisphenol A and epihalohydrin to obtain ethylene oxide-added bisphenol A diglycidyl, and then esterification A catalyst is used to produce ethoxylated bisphenol A di (meth) acrylate as a reaction product with methacrylic acid or acrylic acid.

<Component (D)>
The monofunctional (meth) acrylate monomer used for component (D) is not particularly limited. For example, a monofunctional monomer having a cyclic hydrocarbon group having one carbon-carbon double bond or one nitrogen atom as an alcohol residue in the ring. It is a (meth) acrylate monomer. The molecular weight and properties of the monofunctional (meth) acrylate monomer (D) are not particularly limited, but preferably the molecular weight is 300 or less, more preferably the molecular weight is 240 or more, and the viscosity at 25 ° C. is 100 mPa · s or less. The vapor pressure is preferably 0.5 mmHg or less. This viscosity is, for example, a viscosity measured using a Brookfield viscometer described in 4.4.1 of JIS K6901. Specific examples include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, pentamethylpiperidyl methacrylate, and pentamethylpiperidyl acrylate. Alternatively, two or more types may be used in combination. When two or more types are used in combination, a mixture of two or more types, that is, the number average molecular weight of the whole component (D) is 240 or more, and the viscosity at 25 ° C. of the whole component (D) is 100 mPa · s or less, The vapor pressure is preferably 0.5 mmHg or less. Among these, the present invention is selected from the group consisting of dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl methacrylate, and pentamethylpiperidyl methacrylate because of its low odor, reactivity, and properties of the cured product. It is preferable to use any one or more of them.

  The usage-amount of the said component (D) is 15-50 mass% with respect to 100 mass% (100 mass parts) of the total amount of a component (A), (B), (C), and (D), Preferably it is 30-50. It is the range of mass%. When there is too little usage-amount of (D), the surface touch dryness of the hardened | cured material after hardening a curable resin composition will be inferior, and the viscosity of a curable resin composition will be high, and it will be inferior to workability | operativity. Moreover, when there is too much usage-amount of (D), when it immerses in high temperature water, a swelling will generate | occur | produce on the surface of hardened | cured material and it will be inferior to durability.

<Ingredient (E)>
Component (E) is a (meth) acrylate monomer having a phenyl group and is not particularly limited. Specific examples thereof include benzyl (meth) acrylate monomer, phenoxyethyl (meth) acrylate monomer, and phenol ethylene oxide (EO). Modified (meth) acrylate, nonylphenyl carbitol (meth) acrylate, nonylphenol EO modified (meth) acrylate, phenoxypropyl (meth) acrylate, phenol propylene oxide (PO) modified (meth) acrylate, (meth) acryloyloxyethyl phthalate, etc. Is mentioned. Among these, phenoxyethyl (meth) acrylate is preferably used in consideration of the odor of the monomer. By using a (meth) acrylate monomer having a phenyl group, a cured product having sufficient tensile strength is obtained, and further a cured product having excellent durability such as water resistance, heat deterioration resistance, and weather resistance is obtained.

  The amount of the component (E) used is preferably in the range of 1 to 10% by mass with respect to the total amount of 100% by mass of the components (A), (B), (C) and (D), and is less than 1% by mass. The cured product of the resin composition is inferior in tensile strength, and the viscosity of the curable resin composition is increased, resulting in inferior workability. When the usage-amount of a component (E) exceeds 10 mass%, the water resistance of a hardened | cured material and heat-resistant deterioration property will be inferior.

<Other ingredients>
The resin composition of the present invention can be used only with the above components (A) to (E), but other components can also be added. When the curable resin composition is used as two or more drugs (eg, main and auxiliary main agents), these other components may be added to any one or more drugs. Specific examples of other components will be described below. In addition, the mixture ratio (mass part) of components other than (A) to (E) is a value based on a total of 100 parts by mass of (A), (B), (C), (D), and (E). It is.

  Resin that significantly reduces cross-linkable polymerizable monomers by using the following cross-linkable polymerizable vinyl monomers together when considering the styrene emission concentration regulations such as the sick house problem and chemical substance release control and transfer registration method (PRTR method) It may be used as a composition.

  Examples of the polymerizable vinyl monomer for crosslinking include aromatic styrene, vinyl toluene, α-methylstyrene, and the like. Further, methacrylic methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and the like can be mentioned. These crosslinking polymerizable monomers may be used alone or in combination of two or more, but generally styrene is used.

  The total amount of the crosslinkable polymerizable monomers (C) and (D) is preferably 40% by mass to 50% by mass with respect to the total 100% by mass of (A), (B), (C) and (D). . On the other hand, the content of the crosslinking polymerizable monomer (X) (such as styrene described above) other than (C) and (D) is 100% by mass in total of (A), (B), (C) and (D). It is 30% or less with respect to this, and 40 mass% or less is preferable with respect to a total of 100 mass% of a crosslinkable monomer (C), (D), (X). In a normal curable resin composition, the content of the crosslinkable polymerizable monomer of the vinyl ester resin is 40 to 50% by mass. For this reason, if the curable resin composition of the present invention is used, the content of the crosslinkable polymerizable monomer is greatly reduced, and it can be applied as a low crosslinkable polymerizable monomer-containing resin composition capable of significantly reducing the amount of volatilization during operation. it can.

In addition to the essential components (A) to (E), a photopolymerization initiator can be added to the curable resin composition of the present invention and cured by photopolymerization. The photopolymerization initiator is not particularly limited, and one or more known ones can be used. For example, there are an ultraviolet polymerization initiator and / or a visible light polymerization initiator. It can also be used to cure thick film fiber-containing curable composite materials. Examples of UV polymerization initiators include benzoin ethers (isopropyl benzoin ether, isobutyl benzoin ether, benzoin ethyl ether, benzoin methyl ether), benzyl ketals (hydrocyclohexyl phenyl ketone, benzyl methyl ketal), ketone benzophenone ( Benzyl, methyl-O-benzoin benzoate, 2-chlorothioxanthone, methyltooxanthone), benzophenone (benzophenone), tertiary amine, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone, acylophosphine oxide, bisacyl Typical examples include phosphine oxide and camphorquinone. When using the curable resin composition of this invention for a photocurable lining material, the coating method of irradiating the surface of a lining material with an ultraviolet-ray and rapid-curing is employable. In this case, a photopolymerization initiator having absorption from the ultraviolet wavelength region to the visible light wavelength region (for example, 250 nm to 450 nm) is preferable. In particular, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzylmethyl ketal are preferable, and these may be used alone or in combination.

  As a visible light polymerization initiator, for example, an acylphosphine oxide compound is effective. Specific examples thereof include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl). There are -4-ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylbenzylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and these are used alone Alternatively, two or more kinds may be used in combination.

  The usage-amount of a photoinitiator is 0.01-20 mass parts with respect to 100 mass parts of total amounts of component (A), (B), (C), (D), and (E), More preferably, it is 0. The range is from 5 to 2.5 parts by mass. If the amount is less than 0.01 parts by weight, the polymerization may not be sufficiently performed. If the amount exceeds 20 parts by weight, the curing time is almost flat, and the curing rate is not improved.

  A prepreg sheet can be formed by adding a thickener to the curable resin composition of the present invention and adjusting it to a suitable viscosity. The thickener is not particularly limited, and for example, any one or more selected from the group consisting of alkaline earth metal magnesium oxide, magnesium hydroxide, potassium oxide, calcium hydroxide, and metal alkoxides may be used. Is possible. Examples of metal alkoxides include aluminum isopropylate, methyl acetoacetate aluminum dibutyrate, methyl ethyl acetoacetate aluminum isopropylate, ethyl acetoacetate aluminum diethoxyethylate, ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate). ). Furthermore, it is also possible to use alone or a mixture of two or more of isocyanates such as toluylene diisocyanate and diphenylmethane diisocyanate in combination with the antari earth metal.

  Alkaline earth metal oxides (such as magnesium oxide) commonly used in styrene-type unsaturated polyester resins and vinyl ester resins increase the viscosity by causing intermolecular crosslinking between the carboxyl groups that are released from the resin composition. However, since the crosslinking reaction is slow, a method of aging in a temperature environment of 40 ° C. or higher is usually employed after the resin composition is impregnated into the fiber and then the thickening is promoted. On the other hand, since the low odor photocurable resin composition (that is, the curable resin composition of the present invention) has no free carboxyl group and has no thickening effect, the thermoplastic resin is used as the curable resin composition. A method of adding and dissolving at a thickening temperature of 50 to 90 ° C. to exert a thickening effect can be employed. The thermoplastic resin as the thickener is preferably added in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the curable composition (that is, a total of 100 parts by mass of the components (A) to (E)).

The curable resin composition of the present invention uses a known thermoplastic resin powder as the thickener. The average single particle size (average primary particle size) of the thermoplastic resin powder is 0.1 to 5.0 μm, preferably 0.2 to 3.0 μm. When the average fine particle diameter is less than 0.1 μm, the fine fine powder ends, the (D) component monofunctional (meth) acrylic monomer absorbs at room temperature quickly, and the viscosity becomes too high. There is a risk that impregnation into the resin becomes difficult. When the average single particle diameter exceeds 5.0 μm, the absorption rate of the (D) monofunctional (meth) acrylic monomer becomes slow, and the pseudo-curing becomes slow. The thermoplastic resin as the thickener preferably has a weight average polymerization degree of 1000 to 150,000. When the weight average degree of polymerization exceeds 150,000, the absorption rate of the monofunctional (meth) acrylic monomer (B) becomes slow, and it is difficult to impart thickening even after a long time. On the other hand, when the molecular weight is less than 1,000, the absorption rate of the monofunctional (meth) acrylic monomer is high and the viscosity is rapidly increased, so that the impregnation of the fibrous material becomes uneven, resulting in the mechanical strength of the prepreg cured product. Is low, and the chemical resistance is remarkably lowered. Further, when the thermoplastic resin powder is copolymerized with a crosslinkable monomer, if the degree of crosslinking is too high, it tends to take a long time to form a prepreg sheet imparting suitable viscosity. Therefore, the degree of crosslinking is preferably such that the insoluble gel component when the thermoplastic resin powder is dissolved in a solvent is 50% by weight or less.

  As a method for producing the thermoplastic resin powder, a known method can be adopted, for example, disclosed in JP-A-9-188770. The thermoplastic resin powder is roughly divided into a homogeneous component polymer (homopolymer), a copolymer of two or more monomers, and a core / shell structure. The thermoplastic resin powder is divided into a curable resin composition, The mixture mixed with the (meth) acrylic monomer, which is one of the components, has a low viscosity immediately after mixing adjustment, rapidly increases in viscosity after the addition of the fibrous material, and thereafter exhibits stability over time of the viscosity.

  As disclosed in JP-A-9-174781, the thermoplastic resin powder is not particularly limited as long as it absorbs a monofunctional (meth) acrylic monomer and swells, but acrylic ester, methacrylic acid. Heat having at least 50% by weight of at least one monomer unit selected from the group consisting of an ester and an aromatic vinyl compound, and having 1 to 20% by weight of a carboxyl group or epoxy group-containing monomer unit It is preferably a plastic resin powder. Examples of the acrylic acid ester used as a raw material monomer for the thermoplastic resin powder include methyl acrylate, ethyl acrylate, n-pyrrolyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, sec-butyl acrylate, 2- One or more selected from the group consisting of ethylhexyl acrylate, n-octyl acrylate, and the like can be used. Examples of the methacrylic acid ester include one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and n-octyl methacrylate. It can be used suitably. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, divinylbenzene, and monomers in which a benzene nucleus of these monomers is substituted with a methyl group, an ethyl group, a propyl group, a butyl group, for example, And vinyltoluene and isobutylstyrene. These monomers can be used alone or in combination of two or more. If the content of the monomer units of these acrylic acid ester, methacrylic acid ester or aromatic vinyl compound in the thermoplastic resin powder is less than 50% by weight, the thermoplastic resin powder may not exhibit a sufficient thickening effect. There is.

The thermoplastic resin powder, which is a component for imparting thickening of the curable resin composition of the present invention, may contain other monomer units copolymerizable with the above-mentioned monomers. As monomers, vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl oleate, vinyl benzoate; acrylic acid, methacrylic acid, 2 -Unsaturated dicarboxylic acids such as ethyl propionic acid, crotonic acid and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, citraconic acid and chloromaleic acid; monomethyl maleate, monomethyl maleate and monoethyl maleate Monoesters of unsaturated dicarboxylic acids such as monobutyl itaconate; butadiene, isoprene, 1, - pentadiene, conjugated diene compounds such as cyclopentadiene; 1,4-hexane and the non-conjugated diene compounds such as dicyclopentadiene and the like. Furthermore, in order to adjust the solubility when the thermoplastic resin powder is used as a thickener in the process of preparing the prepreg of the curable vinyl ester resin composition, the polymer constituting the thermoplastic resin powder is appropriately crosslinked. can do. Examples of the copolymer component for giving a crosslinked structure include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2 -Aminobutyl (meth) acrylate, (meth) acrylamide, N-2-aminopropyl (meth) acrylate, N-2-aminoethyl (meth) acrylamide, N-3-aminopropyl (meth) acrylamide, ethylene group number 1 -14 monomers such as polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triallyl trimellitate, diallyl phthalate, allyl glycidyl ether, triallyl isocyanurate, and the like. The amount of these crosslinkable monomers should not exceed 0.5% by weight in the copolymer. If the degree of crosslinking is too high, the absorption rate is slow, and the predetermined thickening effect cannot be exhibited. As the other copolymerizable monomer, only one kind can be used, or two or more kinds can be used in combination. There is no restriction | limiting in particular about the manufacturing method of thermoplastic resin powder, A well-known method is employable, For example, the method used for manufacture of fine resin powders, such as polymethylmethacrylate shown by Unexamined-Japanese-Patent No. 9-188770 For example, a fine suspension polymerization method, an emulsion polymerization method, a seeding emulsion polymerization method, or the like can be employed. Among these methods, a polymerization method that can obtain a spherical particle size without being extremely fine is particularly preferable. For example, as the fine suspension polymerization method, a surfactant or a dispersant is usually used. Examples of the surfactant include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate; sodium dioctylsulfosuccinate and dihexylsulfosuccinate. Sulfosuccinic acid ester salts such as sodium acid salt; fatty acid salts such as ammonium laurate and potassium stearate; polyoxyethylene alkylsulfuric acid ester salts, polyoxyethylene alkylarylsulfuric acid ester salts; and anionic surface activity such as sodium dodecyl diphenyl ether disulfonate Agents: Sorbitan monooleate, sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc. Ethers; nonionic surfactants such as polyoxyethylene alkyl ethers; cetylpyridinium chloride, and the like cationic surface active agents such as cationic, such as cetyltrimethylammonium bromide. Examples of the dispersant include polyvinyl alcohol, methyl cellulose, and polyvinyl pyrrolidone. These surfactants and dispersants can be used alone or in combination of two or more. The amount used can be appropriately selected in the range of 0.05 to 10 parts by weight, preferably 0.2 to 7 parts by weight, per 100 parts by weight of the monomer used.

  Methods for producing thermoplastic resin powders are roughly classified into homogeneous component polymers (homopolymers) such as the above-mentioned JP-A-9-188770, copolymers of two or more monomers, and core / shell structures. The thermoplastic resin powder used in the present invention has a core / shell structure having a shell layer containing a polymer containing 1 to 20% by weight of a carboxyl group-containing monomer unit or an epoxy group-containing monomer unit. can do. When the core component is a (meth) acrylic acid ester polymer and / or diene copolymer having a glass transition point of −30 ° C. or lower, preferably −40 ° C. or lower, the mechanical strength and elastic modulus of the molded product. Is preferable because it is greatly improved.

  Although it is the characteristic that only the components (A) to (E) of the resin curable composition of the present invention are excellent in drying property, paraffin and / or waxes may be used in combination for the purpose of improving drying property. Good.

  As the paraffin and / or wax, one or more selected from waxes such as paraffin wax and polyethylene wax, higher fatty acids such as stearic acid and 1,2-hydroxystearic acid can be used, but preferably Paraffin wax is used. Paraffin and / or waxes are added for the purpose of improving the air blocking effect and the stain resistance during the curing reaction on the coating film surface. As an addition rate, it is 0.1-5 mass parts with respect to 100 mass parts of resin compositions of component (A), (B), (C), (D), and (E), Preferably it is 0.2-2 mass. Part.

  An inert fine particle and / or powdery inorganic aggregate material (inorganic material) can be further added to the curable resin composition of the present invention. Such inorganic aggregate materials include sand, silica powder, ground rock, calcium carbonate, alumina powder, clay, silica powder, talc, glass powder, silica powder, aluminum hydroxide, silica sand, aluminum silicate, magnesium silicate, cement Etc. can be used.

  Further, the amount of the inorganic aggregate material used depends on workability such as desired fluidity and is determined by the strength of the cured product of the concrete composition, but the addition rate is that of the curable resin composition. It is set as the range of 100-600 mass parts with respect to 100 mass parts, Preferably it is 150-600 mass parts. The average particle size of the inorganic aggregate material is 0.02 mm to 10 mm, preferably 0.05 mm to 5 mm. In addition, the aggregate is No. 1 silica sand (average particle size 5 to 2.5 mm), No. 2 silica sand (particle size 2.5 to 1.2 mm), No. 3 silica sand (particle size 1) defined in JIS G5901-1968. .2 to 0.6 mm), No. 4 silica sand (particle size 0.6 to 0.3 mm), No. 5 silica sand (grain sand 0.3 to 0.15 mm), No. 6 silica sand (grain sand 0.15 to 0.3 mm). 074 mm) and No. 7 silica sand (particle size of 0.074 mm or less) can also be used.

  Inactive fine particles used in the present invention include calcium carbonate, fly ash, clay, alumina powder, silica powder, talc, silica powder, glass powder, mica, aluminum hydroxide, aluminum silicate, magnesium silicate, cement, marble, etc. Is preferred. The average particle diameter of the fine particles is preferably about 0.5 μm to 20 μm. The addition rate of the inactive fine particles (inorganic aggregate material) is 2.5 to 100 parts by mass with respect to 100 parts by mass of the curable resin composition (100 parts by mass in total of components (A) to (E)). It is preferable to be added. Moreover, an inorganic aggregate material may be used individually by 1 type, and may use 2 or more types together.

  To the curable resin composition of the present invention, 5 to 50 parts by mass of a flaky inorganic filler is added to 100 parts by mass of the resin composition (100 parts by mass of components (A) to (E)). It can also be a concrete lining material.

  Examples of the scale-like inorganic filler include glass flakes and mica flakes. Among these, it is more preferable to use glass flakes. As the flaky inorganic filler, those having an average particle diameter of 10 to 4000 μm can be usually used, but in order to keep the workability of the concrete composition satisfactorily, the average particle diameter is in the range of 100 to 1000 μm. It is more preferable to use one.

  It is preferable to add an organic peroxide to the curable resin composition of the present invention. The organic peroxide includes ketone peroxides (for example, methyl ethyl ketone peroxide); hydroperoxides (for example, cumene hydroperoxide, t-butyl hydroperoxide, etc.); peroxy esters (for example, t-butyl peroxide). One or more known substances such as octoate, t-butylperoxybenzoate); dialkyl peroxides (eg dicumyl peroxide); diacyl peroxides (eg lauroyl peroxide, benzoyl peroxide) To use.

  The amount of the organic peroxide used is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the essential components (A), (B), (C), (D) and (E). .

The present invention further provides 0.01 to 5 parts by mass of other additives (aromatic amine-based accelerators based on 100 parts by mass of the resin composition (that is, 100 parts by mass in total of components (A) to (E)). Agent and / or polyvalent metal salt and / or complex) and then mixed with an organic peroxide to form a thermosetting resin composition. In this case, the lining material is particularly effective for promoting curing. . If the addition amount of the other additives is less than 0.01 parts by mass, curing is not sufficient, and if it exceeds 5 parts by mass, no further effect is exhibited.

  As the aromatic amine accelerator, one or more combinations of aniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, N, N-dimethyl-P toluidine and the like can be used.

  Among the polyvalent metal salts and / or complexes, the polyvalent metal salt is, for example, naphthenic acid, octenoic acid, and the like, and the polyvalent metal is calcium, copper, manganese, cobalt, vanadium, or the like. Particularly preferred are cobalt octylate and cobalt naphthenate.

  Examples of the complex include acetylacetone, cobalt acetylacetonate, and manganese acetylacetonate.

  In addition, one or more additional additives such as pigments, antioxidants, flow control agents, thixotropic agents, and plasticizers may be added to the above-described resin composition, concrete coating composition, and lining material as necessary. Is also possible.

  For repair of an aged sewerage treatment facility, usually a primer is applied after applying a cross-section repair material to the wall thickness of the existing deteriorated concrete structure wall, and then a new substrate preparation material for the purpose of unevenness adjustment. A method of applying a coating type resin lining material is used. In the case of newly installing a structure, a method is used in which a primer is applied to a concrete base, and then an anticorrosion-coated resin lining material is applied after applying a base material for the purpose of adjusting unevenness.

  Conventionally, a moisture-curing urethane primer or the like has been used as the above-mentioned primer, and this urethane primer is used to improve the solubility, viscosity reduction, and drying properties of solvents such as toluene and xylene and urethane resin. However, toluene and xylene are substances subject to the Poisonous and Deleterious Substances Control Law (Ministry of Health, Labor and Welfare) and the Odor Control Law (Ministry of the Environment). Are also listed. In addition, it is a Class 1 Designated Chemical Substance by PRTR (Ministry of Economy, Trade and Industry and Ministry of the Environment), and since 2002, the Ministry of Education, Culture, Sports, Science and Technology has been obligated to measure the concentration when handing over new construction or renovation work. In this way, it is expected that these solvents will become more restrictive in the future. As a countermeasure against the above-mentioned toluene and xylene, a system using an aqueous blimmer or a non-aromatic solvent has been proposed, but the former is impregnated into foundation concrete, wettability, poor drying in low temperature environment in winter, adhesion If the non-aromatic solvent remains in the primer layer without volatilizing, it causes a dullness of the upper layer coating material, and there are problems such as a long time to dry the touch after applying the primer.

  Moreover, as a curable resin composition used for a coating-type resin lining material, an unsaturated polyester resin composition has been conventionally used. Recently, an unsaturated monobasic acid, particularly acrylic acid or an epoxy resin is used as an epoxy resin. A resin composition (generally a vinyl ester resin composition) containing an epoxy (meth) acrylate obtained by reacting methacrylic acid is used.

In known unsaturated polyester resin compositions and vinyl ester resin compositions used for coating type lining materials, styrene monomers are generally used as copolymerizable monomers. However, since this mixture of ester and styrene has a peculiar odor and diffuses to the environment around the construction, a method of adsorbing the generated styrene with an activated carbon adsorption device has been introduced. In addition, as described above, styrene needs to be managed by the PRTR system or specified by a specified chemical substance (Ministry of Health, Labor and Welfare), and regulations on the styrene concentration in the resin are becoming strict.

  As a measure against styrene regulation, a conventional non-styrene type vinyl ester resin primer disclosed in JP-A-2002-60282, JP-A-10-231453, JP-A-2000-63448, JP-A-2000-63449, etc. is applied to a concrete structure. It is possible to apply a lining material containing the curable resin composition of the present invention after application to (deteriorated concrete or new concrete) to form an anticorrosion coating layer, but the curable resin composition of the present invention ( It is preferable to use the components (A) to (E)) as a primer material.

  That is, since the entire process from the primer to the anticorrosion coating layer is formed with a non-styrene resin composition using the curable resin composition of the present invention, the above legal restrictions are eliminated, and low odor, water resistance, It becomes possible to provide a curable resin composition excellent in chemical resistance, durability, adhesion, and air drying properties.

  In addition, pigments, antioxidants, flow control agents, thixotropic agents, plasticizers, and the like can be added to the resin composition and lining material of the present invention as necessary.

Next, another example of the lining material of the present invention will be described.
In the present invention, (F) hydraulic cement and (H) cement together with any one or more of the above-described components (scalar inorganic filler, organic peroxide, other additives, etc.) or separately from these components The lining material which added the water reducing agent to the curable resin composition containing component (A)-(E) is also provided.

  Note that (F) hydraulic cement refers to cements that harden or congeal when mixed with water, and (G) water is required to cure (F) lining materials containing hydraulic cement. (G) Water does not need to be contained in the lining material as a product, and may be added immediately before use.

<Component (F)>
Although hydraulic cement is not specifically limited, For example, Portland cement and rapid hardening type cement with high alumina content are preferable. As the Portland cement, various kinds of cements such as ordinary Portland cement, early-strength Portland cement, white Portland with low iron and carbon content, and other cements as described below can be used.

  Other cements include low heat (Portland) cement, which has high water content of dicalcium silicate and tetracalcium aluminoferrite and low content of tricalcium silicate and tricalcium aluminate; calcium tricalcium silicate Sulfate-resistant (Portland) cement characterized by an unusually high content of calcium and dicalcium silicate and an unusually low content of tricalcium aluminate and tetracalcium aluminoferrite; Portland cement clinker and granular Portland Plast Furnace Cement, characterized by its mixture with mineral slag; Portland cement and hydrated lime, granular slag, ground limestone, colloidal clay, diatomaceous earth, or other silica, calcium stearate and paraffin fines A mixture of one or more selected from Masonry cement, characterized by being a natural cement; natural cement, characterized by being obtained from natural sediments such as Lehigh Valley in the United States; a pure or impure form of calcium oxide, Selenite cement characterized by the presence or absence of some soil material; characterized by volcanic ash, volcanic ash diatomaceous earth, pumice, limestone, santrin earth, or a mixture of granular slag and lime mortar Volcanic ash mixed cements; calcium sulfate cements characterized by containing calcium sulfate hydrate and gypsum plaster.

  (F) Although the usage-amount of hydraulic cement is not specifically limited, A preferable usage-amount is 5 with respect to a total of 100 mass parts of (A), (B), (C), (D) component of curable resin composition. It is -300 mass parts, More preferably, it is 10-200 mass parts, Most preferably, it is 20-100 mass parts. (F) Even when hydraulic cement is used, preferred amounts of the components (A), (B), (C), (D), and (E) are the same as those of the curable resin composition and other lining materials. It is. That is, the preferable amount with respect to a total of 100 parts by mass of the components (A), (B), (C), and (D) is 1 to 10 parts by mass of the (E) component, 10 to 50 parts by mass of the (A) component, The component (B) is 5 to 50 parts by mass, the component (C) is 3 to 30 parts by mass, and the component (D) is 15 to 50 parts by mass. The mass ratio of the component (A) and the component (B) is preferably for the above-described soft cured product, that is, the mass ratio (A) / (B) is 70/30 or more and less than 95/5.

<Ingredient (H)>
In the lining material of the present invention, a generally used (H) cement water reducing agent can be widely used, and this cement water reducing agent is preferably used when the component (G) is used. (H) Cement water reducing agent is usually used for the purpose of preventing deterioration of fluidity and air volume of concrete, mortar or cement paste, which is a hydraulic cement compound, over time, and improving its workability and workability. The

  The cement water reducing agent is not particularly limited, and one or more known water reducing agents can be used. Specifically, naphthalene sulfonate formaldehyde condensate water reducing agent; melamine sulfonate formaldehyde condensate water reducing agent; Carboxylic acid type water reducing agent; Lignin sulfonic acid type water reducing agent; Polystyrene sulfonic acid type water reducing agent; Phenol formaldehyde condensate type water reducing agent: and aniline sulfonic acid type water reducing agent, and these acid salt type water reducing agents and their acid esters A cement water reducing agent for at least one cement selected from the group consisting of water reducing agents (eg, carboxylates, carboxylic esters, sulfonates, sulfonates) can be preferably used.

  These water reducing agents are basically water-soluble, exhibit surfactant-like properties having a hydrophobic part and a hydrophilic part in the molecule, and are dispersed liquids containing (F) cement and (G) water. It plays the role of an emulsifier that stably disperses the lining material.

  That is, when a first component containing (A), (B), (C), (D) and (E) and a second component containing (F) hydraulic cement are mixed, (H) cement water reducing agent By coating the surface of the cement particles (F), in particular, (G) dispersion in water can be promoted and a uniform mixed solution can be improved.

  The amount of the (H) cement water reducing agent used is 0.01 to 20% by mass, preferably 0.1 to 15% (when the mass of the hydraulic cement is 100% by mass) relative to (F) the hydraulic cement. % By weight, and (F) 0.1 to 5 parts by weight is particularly preferable with respect to 100 parts by weight of the hydraulic cement. The By adjusting the amount of use, when the cement composition of the present invention is cured, a good dispersion and mixing effect that ensures adequate workability can be obtained.

  The component liquids of (B), (C), (D), and (E) excluding (A) have a large effect on the inhibition of curing by moisture, and (F) hydraulic cement, (G) water, and (H) cement When a mixed component liquid of a water reducing agent is added, there is a drawback that sufficient strength, chemical resistance and adhesiveness cannot be obtained.

  The amount of (G) water used in the present invention is preferably 5 to 1000 parts by mass, more preferably 100 to 1000 parts by mass, and particularly preferably 10 to 500 parts by mass with respect to 100 parts by mass of (F) hydraulic cement.

  (F) When using hydraulic cement, the above-mentioned inorganic aggregate material can be used, and other known inorganic aggregates and organic aggregates can also be used. Preferred inorganic aggregates include natural siliceous materials such as river sand and silica sand; various types such as those obtained by pulverizing inorganic materials such as glass, ceramics, fused alumina and silicon carbide; hollow materials such as glass balloons and shirasu balloons One or more types can be selected and used.

  The inorganic aggregate preferably has a particle size of 0.05 mm to 4 mm. These materials may be in a natural state, for example, artificially colored by using dyes or pigments. As the organic aggregate, a pulverized product of plastic can be used. The aggregate content is preferably 10 to 2000 parts by mass, more preferably 25 to 1000 parts by mass, and particularly preferably 100 to 700 parts by mass with respect to 100 parts by mass of (F) hydraulic cement.

  Furthermore, when using the said (F) and (H) component, it is more preferable to add an organic peroxide.

  Next, although an example of the present invention explains, the present invention is not limited to this. In the examples, “part” is “part by mass” unless otherwise specified.

[ Reference Example 1 ]
<Manufacture of urethane methacrylate (A)>
A four-necked flask equipped with a stirrer, a reflux tube, a dropping funnel, and a gas introduction tube was charged with 60.97 g of Actol D-400 (Mitsui Chemicals) and 124.45 g of Actol D-700 (Mitsui Chemicals), and 100 under reduced pressure. The mixture was dehydrated at 0 ° C., the water content was adjusted to 0.016% or less, and then cooled to 60 ° C. or less. To this was dropped 114.7 g of 2,6-toluene diisotosocyanate (Cosmonate T-80: Mitsui Chemicals) as an aromatic diisocyanate compound at room temperature over 1 hour, and the internal temperature was maintained at 80 ° C to 85 ° C. While reacting. After the NCO group content reaches 9.23% or less, it is cooled to 50 ° C. or lower, and then 0.05 g of hydroquinone and 99.67 g of hydroxypropyl methacrylate (Nippon Catalyst) are added dropwise and maintained at 50 ° C. to maintain dibutyl tin. 0.14 g of dilaurate was added, the reaction temperature was kept at 60 ° C., and the reaction was continued until the absorption of the NCO group of 2270 cm ⁻¹ disappeared in the infrared absorption spectrum to obtain urethane methacrylate (A).

<Production of aromatic epoxy methacrylate (B) having a number average molecular weight of about 750>
148 g of jER828 (Mitsubishi Chemical), 360 g of jER1001 (Mitsubishi Chemical) and 240 g of jER1002 were charged into a 2 liter four-necked flask equipped with a stirrer, condenser, thermometer and air introduction tube, and 10 liters of dry air per minute with stirring. The temperature was raised to 130 ° C. while blowing. After the temperature increase, 148 g, hydroquinone (polymerization inhibitor) 0.3 g, and trimethylbenzylammonium chloride 2 g were added, and 172 g of methacrylic acid was added dropwise over 2 hours. After 3 hours from the end of dropping, measurement of the acid value was started every hour, and after confirming that it was 10 KOHmg / g or less, the mixture was cooled to 100 ° C. and aromatic epoxy methacrylate (B). A certain bisphenol A diglycidyl ether methacrylic acid adduct was obtained.

<Formulation of curable resin composition>
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (C) (Shin Nakamura Chemical Co., Ltd.) was added to 40 parts by mass of urethane methacrylate (A) and 10 parts by mass of aromatic epoxy methacrylate (B) obtained in the above production. BPE-100) 15 parts by mass, dicyclopentenyloxyethyl methacrylate (D) (Hitachi Chemical Industry Co., Ltd. FA-512MT) 35 parts by mass of (A), (B), (C) and (D) total 100 parts by mass 5 parts by mass of phenoxyethyl methacrylate (E) (Kyoeisha Chemical Co., Ltd., Light Ester PO) was added to the solution and dissolved, and then cooled to room temperature to obtain a curable resin composition of Reference Example 1 .

  Next, an evaluation test method for each curable resin composition will be described. This curable resin composition was used as the base composition (I) and used in the following tests with the following composition.

Glass flake RCF140: Nippon Sheet Glass Co., Ltd. Silica stone powder: Crystallite AA, Tatsumori Co., Ltd. Percure-K: NOF Corporation

<Test conditions>
The composition (II) was mixed well, then poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. This resin cured product was subjected to a bending test (elastic modulus) at a test speed of 1000 mm / min according to JIS K6901.

  The tensile test (elastic modulus and elongation) was measured according to JIS K7113. In the laminate for this tensile test, FRP having a glass content of 30% was laminated on a release-treated glass plate using 3 plies of chop strand mat MC-450 (manufactured by Nitto Boseki Co., Ltd.). Cured at 25 ° C. for 72 hours to obtain a laminate.

The bending strength (elastic modulus) was measured according to JIS K6911, and the tensile strength (tensile elastic modulus, elongation) was measured according to JIS K7113. The Barcol hardness and sulfur penetration depth were measured by the above methods.

As for the surface drying time, a coating film was prepared on a glass plate at room temperature of 20 ° C. using an applicator, and a finger touch test was performed on the surface drying property. The evaluation method measured the time until the absorbent cotton did not remain on the coating film surface due to adhesion even when about 2-3 cm ² of absorbent cotton was pressed against the coating film surface.

  The concrete adhesion strength was tested according to JIS A6916 with a Kenken tensile tester, and the adhesive strength was measured.

In the concrete peeling test, a primer layer, a base material adjusting material, and a surface protective layer were laminated on a JIS A 5304 standard sidewalk board (size: 300 mm × 300 mm) according to the formulation shown in Table 1 above. More specifically, using a curable resin composition of Reference Example 1 (in the case of Reference Examples 2 to 4 and Examples 1 to 4 , the resin composition of each example was used), a resin composition (primer: After applying 150 g / m ^{2 of the} coating amount in the “Primer” column of Table 1 and confirming the drying by touching with a finger, 700 g / m ² of the composition of the “base material preparation” in Table 1 was applied. After confirming drying by touching with a finger, the composition of the “surface protective layer” in Table 1 was further applied at a coating amount of 1 kg / m ² (thickness 0.6 mm) to complete the anticorrosion coating layer. It was. After curing at 25 ° C. for 72 hours, an FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm was bonded with an epoxy adhesive leaving an unadhered portion 20 mm at one end in the length direction. A hole with a diameter of 2 mm was formed in the center of the unbonded portion, a hook at the tip of a spring balance was inserted into this hole, and 90 ° peeling was measured in accordance with the vulcanized rubber adhesion test method of JIS K6256.

  The weight change rate was determined by pouring 10 g of the sufficiently mixed composition (II) in Table 1 into a glass petri dish having a diameter of 40 mm (height: 15 mm), curing the mold at 25 ° C. for 72 hours, and then removing the cast from hot water (80 C.) for 96 hours, and the weight change rate before and after immersion was measured. As for the volatilization amount of styrene, 100 g of the sufficiently mixed composition (II) in Table 1 was put into a glass petri dish having a diameter of 145 mm, and the weight change rate was measured after 60 minutes.

  The amount of wear was measured by the wear wheel method of JIS A1453 (abrasion test method (abrasive paper method) for building materials and building components) under the conditions of a wear wheel CS-17, a load of 1 kg, and a rotation speed of 1,000 rpm.

  The number average molecular weight described in the examples was measured by high performance liquid chromatography (GPC) and indicated as a polystyrene equivalent value.

  The method for measuring the Barcol hardness in the hardness test is defined in the Barcol hardness test method of JIS K7060 (glass fiber reinforced plastic).

  EPMA (electron beam microanalyzer) was obtained by immersing the laminate in a 10% sulfuric acid aqueous solution for 120 days and measuring the penetration depth of sulfur in sulfuric acid. Since the gas phase part of the concrete structure of the sewerage facility is placed in a sulfuric acid environment, the life of the resin coating thickness can be predicted from the sulfur penetration depth.

  The method of measuring impact resistance is defined in the falling ball type test method of JIS K5400 (Paint General Test Method), using a laminate, the weight of the weight is 300.0 ± 0.5 g, and the nominal diameter is 25.40 mm. A grade 60 was dropped from the specified height onto the surface of the laminate.

The method for measuring the resistance to cracking of the substrate is as follows: “Serial Suppression Technology and Anticorrosion Technology Guideline for the Sewerage Concrete Structure” (February 2002) Reference Material-2 Solvent-free polyurethane As a crack followability test of the resin quality standard (reference -20), the crack followability was measured by the zero span of reference -57. In the test method, the former Japan Highway Public Corporation JHS417-1999 (quality standard test method for concrete coating material) 4.7 Cracking followability test was applied by replacing “coating film” with “corrosion protection coating layer”.

As for the volatilization amount of styrene, 100 g was put in a glass petri dish having a diameter of 145 mm after thoroughly mixing the resin composition of the blending ratio of Reference Example 1 , and the weight change rate after standing for 60 minutes and before standing was measured.

[ Reference Example 2 ]
The same components (A), (B) and (D) as in Reference Example 1 except that component (C) was replaced with ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (C) (Kyoeisha Chemical Company, BP-6EM). , (E) was used to obtain a curable resin composition under the same conditions as in Reference Example 1 with the formulation in Reference Example 2 column of Table 2.

About the curable resin composition of Reference Example 2, under the same conditions as Reference Example 1 , the bending test (elastic modulus) of the casting, the tensile test (elastic modulus and elongation), and the bending strength (elastic modulus) of the laminated plate , Tensile strength (tensile modulus, elongation), barcol hardness, sulfur penetration depth, surface drying time, concrete adhesion strength, concrete peeling test, weight change rate, styrene volatilization, EPMA, barcol hardness and wear did.

[Example 1 ]
Using the same components as in Reference Example 2 (A) ~ (E) , the proportions described in Example 1 of Table 2, under the same conditions as in Reference Example 1, 2, mixed, dissolved, curable Example 1 A resin composition was obtained. The curable resin composition of Example 1, under the same conditions as in Reference Example 1, bending test (modulus) of the cast material, a tensile test (modulus and elongation), as well as laminates of flexural strength (modulus of elasticity) , Tensile strength (tensile modulus, elongation), barcol hardness, sulfur penetration depth, surface drying time, concrete adhesion strength, concrete peeling test, weight change rate, styrene volatilization, EPMA, barcol hardness and wear did.

[Example 2 ]
Using the same components (A), (B), (C), (D), and (E) as in Reference Example 1 and the formulation in the column of Example 2 in Table 2, Reference Examples 1, 2 and Example 1 Under the same conditions, each component was dissolved and cooled to obtain a curable resin composition of Example 2 . Using this curable resin composition, the bending test (elastic modulus), tensile test (elastic modulus and elongation) of the casting, and the bending strength (elastic modulus) and tensile strength of the laminate under the same conditions as in Reference Example 1. The thickness (tensile modulus, elongation), Barcol hardness, sulfur penetration depth, surface drying time, concrete adhesion strength, weight change rate, styrene volatilization amount, EPMA, Barcol hardness and wear amount were measured.

[ Reference Example 3 ]
Using the same components (A) to (E) as in Reference Example 2 , a total of 100 parts of component (A) 40 parts by mass, component (B) 10 parts by mass, component (C) 15 parts by mass, and component (D) 40 parts by mass. 5 mass parts of phenoxyethyl methacrylate (E) was added with respect to the mass part, and it melt | dissolved and cooled on the same conditions as Reference Examples 1 and 2 and Example 1 and 2, and obtained the curable resin composition.

Under the same conditions as in Reference Example 1 using the resin composition of Reference Example 3 , the bending test (elastic modulus) of the casting, the tensile test (elastic modulus and elongation), and the bending strength (elastic modulus) of the laminate, Tensile strength (tensile modulus, elongation), barcol hardness, sulfur penetration depth, surface drying time, concrete adhesion strength, concrete peeling test, weight change rate, styrene volatilization amount, EPMA, barcol hardness and wear amount were measured. .

Further, with respect to the resin composition of Reference Example 3 , the following resin concrete test was conducted. Resin concrete uses the total amount of components (A) to (E) as a reference for the blending ratio, and for 100 parts by mass of this total amount, 1.0 part by mass of 6% cobalt naphthenate, 0.5 parts by mass of dimethylaniline, Percure-K2.0 parts by mass is added to and mixed with the curable resin composition of Reference Example 3 ((A) to (E)), and then 450 parts by mass of the inorganic aggregate material (mixed silica sand with the composition shown in Table 1). Was added to obtain a formulation. This resin concrete composition was poured into a 40 × 40 × 160 mm mold to prepare a specimen for measuring compressive strength and bending strength. The tensile strength was prepared by pouring into a rod-shaped mold having a diameter of 2.5 cm. The results measured using these specimens are listed in Table 3 below.

[Example 3 ]
Using the same components (A) to (E) as in Reference Example 2 , component (A) 10 parts by mass, component (B), 40 parts by mass, component (C) 10 parts by mass, and component (D) 40 parts by mass. It mixed, 5 mass parts of components (E) were added with respect to this total 100 mass parts, and it melt | dissolved and cooled on the same conditions as the reference example 1, and obtained the curable resin composition.

Using the resin composition of Example 3 under the same conditions as in Reference Example 1 , the bending test (elastic modulus) of the casting, the tensile test (elastic modulus and elongation), and the bending strength (elastic modulus) of the laminate, Tensile strength (tensile modulus, elongation), barcol hardness, sulfur penetration depth, surface drying time, concrete adhesion strength, concrete peeling test, weight change rate, styrene volatilization amount, EPMA, barcol hardness and wear amount were measured. . Furthermore, by using the resin composition of Example 3 were subjected to resin concrete test under the same conditions as in Reference Example 3. The results are listed in Table 3.

[ Reference Example 4 ]
Using the same components (A), (B), (D), and (E) as in Reference Example 1 , ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (C) (Kyoeisha Chemical Co., Ltd. BP-6EM) as component (C) ), Each component was blended according to the blending in the column of Reference Example 4 in Table 2, and dissolved and cooled under the same conditions as in Reference Example 1 to obtain a curable resin composition of Reference Example 4 .

Using this compound, under the same conditions as in Reference Example 1 , the bending strength (elastic modulus), tensile strength (elastic modulus, elongation) of the casting, and bending strength (elastic modulus) of the laminate, tensile The strength (tensile modulus, elongation), Barcol hardness, sulfur penetration depth, surface drying time, surface drying property, concrete adhesion strength, weight change rate, styrene volatilization amount, EPMA, Barcol hardness and wear amount were measured.

For Reference Example 4 , the properties of the composition containing glass flakes (GF) were measured. This characteristic is obtained by adding 100 parts by mass of the resin composition in which (A) to (E) are blended in the composition of Reference Example 4 in Table 2 to 1.0 part by mass of 6% cobalt naphthenate and 0.1% of dimethylaniline. 5 parts by mass and 2.0 parts by mass of Percure-K were added and mixed, and then 25 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) was added to obtain a compound containing glass flakes. This compound was poured into a 40 × 40 × 160 mm mold to prepare a specimen for measuring compressive strength and bending strength. The tensile strength was prepared by pouring into a rod-shaped mold having a diameter of 2.5 cm. The results measured using these specimens are listed in Table 3 below.

[Example 4 ]
The same components (A), (B), (C), (D), and (E) as in Reference Example 1 were used, and each component was blended in the column of Example 4 in Table 2, and the same as in Reference Example 1 It melt | dissolved and cooled on conditions, and the curable resin composition of Example 4 was obtained.

Using the composition of Table 1, under the same conditions as in Reference Example 1 , the bending strength (elastic modulus), tensile strength (elastic modulus, elongation) of the casting, and bending strength (elasticity) of the laminate Rate), tensile strength (tensile modulus, elongation), Barcol hardness, sulfur penetration depth, surface drying time, surface drying property, concrete adhesion strength, weight change rate, styrene volatilization, EPMA, Barcol hardness and wear Was measured.

For Example 4 , the characteristics of the composition containing glass flakes were also measured under the same conditions as in Reference Example 4 . These measurement results are listed in Table 3.

[Comparative Example 1]
When the acid value was confirmed to be 15 mgKOH / g, the component (B) (that is, an aromatic system having an average molecular weight of 750 and an acid value of 15 mgKOH / g) was used under the same conditions as in Reference Example 1 except that it was cooled to 100 ° C. Epoxy (meth) acrylate) was obtained.

40 parts by mass and 10 parts by mass of the same components (C) and (D) as in Reference Example 1 are added to 50 parts by mass of this component (B), respectively, and the total of these (B) to (D) is 100 parts by mass. On the other hand, 10 parts by mass of phenoxyethyl methacrylate (E) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition of Comparative Example 1.

Using the above curable resin composition, under the same conditions as in Reference Example 1 , the bending strength (elastic modulus), tensile strength (elastic modulus, elongation) of the casting, and bending strength (elastic modulus) of the laminate ), Tensile strength (tensile modulus, elongation), Barcol hardness, sulfur penetration depth, surface drying time, surface drying, concrete adhesion strength, weight change rate, styrene volatilization, EPMA, Barcol hardness and wear It was measured.

[Comparative Example 2]
Using the same components (A), (C), and (D) as in Reference Example 1 , for a total of 100 parts by mass of 45 parts by mass of component (A), 45 parts by mass of component (C), and 10 parts by mass of component (D) Then, 5 parts by mass of phenoxyethyl methacrylate (E) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition of Comparative Example 2.

Using the above curable resin composition, under the same conditions as in Reference Example 1 , the bending strength (elastic modulus), tensile strength (elastic modulus, elongation) of the casting, and bending strength (elastic modulus) of the laminate ), Tensile strength (tensile modulus, elongation), Barcol hardness, sulfur penetration depth, surface drying time, surface drying, concrete adhesion strength, weight change rate, styrene volatilization, EPMA, Barcol hardness and wear It was measured.

[Comparative Example 3]
When the acid value was confirmed to be 17 mg KOH / g, the component (B) (that is, an aromatic system having an average molecular weight of 750 and an acid value of 17 mg KOH / g) was used under the same conditions as in Reference Example 1 except that it was cooled to 100 ° C. Epoxy (meth) acrylate) was obtained.

5 parts by mass of the same component (A) as in Reference Example 1 , 50 parts by mass of the above component (B), 2.6 mol of ethylene oxide addition ethoxylated bisphenol A dimethacrylate (C) (Shin-Nakamura Chemical Co., Ltd. BP-100) 15 mass Part, 30 parts by mass of dicyclopentenyloxyethyl methacrylate (D), and 100 parts by mass of these components (A) to (D) are added and dissolved by adding 10 parts by mass of phenoxyethyl methacrylate (E). Then, it cooled to room temperature and obtained curable resin composition.

Using this curable resin composition, under the same conditions as in Reference Example 1 , the bending strength (elastic modulus), tensile strength (elastic modulus, elongation) of the casting, and bending strength (elasticity) of the laminate Rate), tensile strength (tensile modulus, elongation), Barcol hardness, sulfur penetration depth, surface drying time, surface drying property, concrete adhesion strength, weight change rate, styrene volatilization, EPMA, Barcol hardness and wear Was measured.

[Comparative Example 4]
<Production of aromatic epoxy methacrylate (B) having a number average molecular weight of about 1300>
A 2-liter four-necked flask equipped with a stirrer, condenser, thermometer and air inlet tube was charged with 93 g of jER828 (Mitsubishi Chemical), 180 g of jER1002 (Mitsubishi Chemical) and 990 g of jER1004, and 10 liters of dry air per minute under stirring. The temperature was raised to 130 ° C. while blowing. After the temperature increase, 0.3 g of hydroquinone (polymerization inhibitor) and 2 g of trimethylbenzylammonium chloride were added, and 172 g of methacrylic acid was added dropwise over 2 hours. After 3 hours from the end of dropping, measurement of the acid value was started every hour, and after confirming that the value was 17 KOH mg / g or less, the mixture was cooled to 100 ° C. and an aromatic system having a number average molecular weight of about 1300 An epoxy methacrylate product was obtained.

<Formulation of resin composition>
40 parts by mass of urethane methacrylate (A) obtained in the production of Reference Example 1 , 10 parts by mass of the above component (B), 2.6 mol addition ethylene oxide bisphenol A dimethacrylate (C) (Shin-Nakamura Chemical Co., Ltd. BP- 100) 15 parts by mass, 35 parts by mass of dicyclopentenyloxyethyl methacrylate (D) (Hitachi Chemical Industry Co., Ltd. FA-512MT) are mixed, and phenoxyethyl meta is added to 100 parts by mass in total of components (A) to (D). 10 parts by mass of acrylate (E) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition.

Using this curable resin composition, a casting and a laminate were prepared in the same manner as in Reference Example 1, and each characteristic value was measured. Further, other tests were performed in the same manner as in Reference Example 1 .

  The composition obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K to the resin composition of Comparative Example 4 has low adhesion strength to concrete and peeling strength with concrete. The specimens laminated with the materials were immersed in warm water at 80 ° C. for 25 days, and innumerable minute swelling and peeling occurred between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the hot water (80 degreeC) immersion water absorption was as high as about twice that of the resin composition of the present invention.

[Comparative Example 5]
100 parts by mass of styrene type vinyl ester resin (Showa Denko Lipoxy R804), 40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass), 1 part by mass of 6% cobalt naphthenate, and 2 parts by mass of methyl ethyl ketone peroxide (NOF Parmec NS) Part was added to prepare a formulation. When each characteristic test was conducted under the same conditions as in Reference Example 1 using this blend, the styrene volatilization amount was as extremely high as 80 g / m ² . Other measurement results are listed in Table 4.

[Comparative Example 6]
30 parts by mass of urethane methacrylate (A) obtained by the production of Reference Example 1 , 40 parts by mass of an aromatic epoxy methacrylate (B) having a number average molecular weight of 1300 obtained by the production of Comparative Example 4, and 2.6 mol addition ethoxylated ethylene oxide Bisphenol A dimethacrylate (C) (Shin-Nakamura Chemical Co., Ltd. BPE-100) 15 parts by mass and dicyclopentenyloxyethyl methacrylate (D) 15 parts by mass are mixed, and a total of 100 of these components (A) to (D) is mixed. 10 parts by mass of phenoxyethyl methacrylate (E) was added to parts by mass and dissolved, and then cooled to room temperature to obtain a curable resin composition.

Using this curable resin composition, a casting and a laminate were prepared in the same manner as in Reference Example 1, and each characteristic value was measured. Further, other tests were performed in the same manner as in Reference Example 1 .

Resin concrete is prepared by first mixing and mixing 100 parts by mass of the curable resin composition with 1.0 parts by mass of 6% cobalt naphthenate, 0.5 parts by mass of dimethylaniline, and 2.0 parts by mass of Percure-K, and then inorganic bone. 450 parts by mass of material (mixed silica sand having the composition shown in Table 2) was added to obtain a composition. For this blend, the specimen for measuring compressive strength and bending strength is 40 × 40 × 160.
The above composition was poured into a mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold.

[Comparative Example 7]
50 parts by mass of urethane methacrylate (A) obtained by the production of Reference Example 1 , 15 parts by mass of an aromatic epoxy methacrylate (B) having a number average molecular weight of 1,300 obtained by the production of Comparative Example 4, and 30 mol addition ethoxylate of ethylene oxide Bisphenol A dimethacrylate (C) (Shin-Nakamura Chemical Co., Ltd. BPE-1300) 15 parts by mass and dicyclopentenyloxyethyl methacrylate (D) 20 parts by mass are mixed, and a total of 100 of these components (A) to (D) is mixed. 10 parts by mass of phenoxyethyl methacrylate (E) was added to parts by mass and dissolved, and then cooled to room temperature to obtain a curable resin composition.

Using this curable resin composition, each characteristic test was performed under the same conditions as in Reference Example 1 .

  The resin composition containing glass flakes was the blending column in the column of Comparative Example 7 in Table 2. That is, the composition of the resin composition containing glass flakes was obtained by dissolving 3.0 parts by mass of 20% 120 degrees F / (FA-512MT) paraffin wax (solid content of 0.6 parts by mass) in 100 parts by mass of the resin composition. Thereafter, 1.0 mass part of 6% cobalt naphthenate, 0.5 mass part of dimethylaniline, and 2.0 mass parts of Percure-K are first added and mixed, and then glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) 40 A part by mass was added to obtain a blend. This compound was poured into a 40 × 40 × 160 mm mold to prepare a specimen for measuring compressive strength and bending strength, and the compound was poured into a rod-shaped mold having a diameter of 2.5 cm to prepare a specimen for tensile strength.

  In the table, * 1 represents a composition containing glass flakes, * 2 represents methyl ethyl ketone peroxide, and * 3 (presence or absence of irritating odor of resin composition) represents an irritating odor of styrene monomer.

[ Reference Example 5 ]
Reference Example 1 in the same urethane methacrylate (A) 45 parts by mass, the same aromatic epoxy methacrylate as in Reference Example 1 (B) 10 parts by weight, of ethylene oxide 4.0-mole adduct ethoxylated bisphenol A dimethacrylate (C) (New Nakamura Chemical Co., Ltd. BPE-200) 15 parts by mass, dicyclopentenyloxyethyl methacrylate (D) 35 parts by mass total 100 parts by mass, after adding 10 parts by mass of phenoxyethyl methacrylate (E), to room temperature It cooled and the curable resin composition was obtained.

  To 100 parts by mass of the resin composition, 1.5 parts by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO manufactured by BASF) is added as a photopolymerization initiator, and sufficiently stirred, mixed and dissolved. After cooling to room temperature, 30 parts by mass of polymethyl methacrylate resin powder (Ganz Kasei, Zephyak F320) with an average particle size of 1.9 μm and a weight average polymerization degree of 30000 is added and heated to 80 ° C. A curable resin composition for prepreg was obtained.

A polyurethane elastomer film with a thickness of 0.2 mm and 790M60K (manufactured by Nippon Valqua Industries) are laid, and a chop strand mat (REM450-G5; manufactured by Nippon Sheet Glass) with a unit weight of 450 g / m ² is layered thereon for the above prepreg The resin composition was introduced and impregnated, and a polyurethane elastomer film having a thickness of 0.2 mm, 790M60K (manufactured by Nippon Valqua Industries Co., Ltd.) was coated thereon and irradiated with ultraviolet rays (metal halide lamp: Ga series, 240 W, irradiation intensity 80 mW). / Cm ² ) was carried out for 3 minutes to produce a laminate. The physical properties of this laminate are shown in Table 4.

[Example 5 ]
Reference Example 1 in the same urethane methacrylate (A) 10 parts by weight, the same aromatic epoxy methacrylate as in Reference Example 1 (B) 40 parts by weight, of ethylene oxide 4.0-mole adduct ethoxylated bisphenol A dimethacrylate (C) (New Nakamura Chemical Co., Ltd. BPE-200) 10 parts by mass, dicyclopentenyloxyethyl methacrylate (D) 40 parts by mass total 100 parts by mass, after adding 10 parts by mass of phenoxyethyl methacrylate (E), to room temperature It cooled and the curable resin composition was obtained. In 100 parts by mass of the resin composition, 1.5 parts by mass of a photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF's Lucillin TPO) is thoroughly stirred, mixed and dissolved, and then cooled to room temperature. Next, 30 parts by mass of a polymethyl methacrylate resin powder (manufactured by Ganz Kasei Co., Ltd., Zephyak F320) having an average particle diameter of 1.9 μm and a weight average polymerization degree of 30000 is added, heated to 80 ° C., dissolved, and photocurable prepreg resin composition. Got. Using this curable prepreg resin composition, a laminate was produced under the same conditions as in Reference Example 5 . The physical properties of this laminate are shown in Table 4.

[Comparative Example 8]
10 parts by mass of urethane methacrylate (A) as in Reference Example 1 , 50 parts by mass of aromatic epoxy methacrylate (B) as in Comparative Example 4, 2.6 mol of ethylene oxide addition ethoxylated bisphenol A dimethacrylate (C) (new) Nakamura Chemical Co., Ltd. NK Light Ester BPE-1300) 35 parts by mass and dicyclopentenyloxyethyl methacrylate (D) 10 parts by mass in total, 100 parts by mass add phenoxyethyl methacrylate (E) 10 parts by mass to dissolve Then, it cooled to room temperature and obtained curable resin composition. A photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF's Lucillin TPO) 1.5 parts by mass was thoroughly stirred, mixed and dissolved in 100 parts by mass of the resin composition, and then cooled to room temperature. Next, 30 parts by mass of polymethyl methacrylate resin powder (manufactured by Ganz Kasei Co., Ltd., Zephyak F320) having an average particle size of 1.9 μm and a weight average degree of polymerization of 30000 is added and heated and dissolved at 80 ° C. to obtain a photocurable prepreg resin composition. Obtained. Using this curable prepreg resin composition, a laminate was produced under the same conditions as in Reference Example 5 . The physical properties of this laminate are shown in Table 4.

<Hydraulic cement-containing lining material>
Hereinafter, comparative tests were performed on lining materials containing hydraulic cement.

[Example 11]
Using the same components (A), (B), (C), (D), and (E) as in Reference Example 1 , a base composition was produced under the same conditions as in Reference Example 1, and (F) hydraulic cement (Sumitomo) (Example: Osaka Cement Co., Ltd. Hayashi Portland Cement), (G) Water, (H) Cement water reducing agent (SF500H manufactured by Floric Co., Ltd., polycarboxylic acid type) in the proportions shown in Table 6 below. 11 hydraulic resin compositions (lining materials) were obtained. To this hydraulic resin composition, 8% cobalt octylate, dimethylaniline, and organic peroxide (Nyper NS) were further added at the blending ratio described in Example 11 column of Table 6, and then Reference Example 1 and Various evaluation tests were performed under the same conditions.

[Example 12]
A hydraulic resin having a blending ratio shown in Table 6 under the same conditions as in Example 11 except that component (C) was replaced with ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (C) (Kyoeisha Chemical Company, BP-6EM). A composition was obtained. Various evaluation tests were performed on this hydraulic resin composition in the same manner as in Example 11.

[Example 13]
Using the same components (A) to (E) as in Example 12, and under the same conditions as in Example 11, a hydraulic resin composition having a blending ratio shown in Table 6 was obtained. Various evaluation tests were performed on this hydraulic resin composition in the same manner as in Example 11.

[Example 14]
The same ethylene oxide 2.6 mol adduct component (C) as in Example 11 was used, and the mixing ratio described in the column of Example 14 in Table 6 was changed to the hydraulic properties of Example 14 under the same conditions as in Example 11. A resin composition was obtained. Various evaluation tests were performed on this hydraulic resin composition in the same manner as in Example 11.

[Example 15]
The same (A) to (E) as in Example 12 were used, and the mixing ratio described in the column of Example 15 in Table 6 was changed to obtain a hydraulic resin composition under the same conditions as in Example 11. For this hydraulic resin composition, various evaluation tests were conducted in the same manner as in Example 11. Further, the following resin concrete test was also conducted for this hydraulic resin composition.

  Resin concrete is based on the total amount of components (A) to (E), and the total amount of 100 parts by mass is 1.0 part by mass of 8% cobalt octylate solution and 0.5 part by mass of dimethylaniline. Further, 3 parts by mass of Nyper NS (manufactured by NOF, diacyl peroxide) was further added to the hydraulic resin composition of Example 11, and in addition to this, a resin in which 250 parts by mass of an inorganic aggregate material (mixed silica sand) was added. The concrete composition was poured into a 40 × 40 × 160 mm mold to prepare a specimen for measuring compressive strength and bending strength. The tensile strength was prepared by pouring into a rod-shaped mold having a diameter of 2.5 mm. Using these specimens, an evaluation test was performed in the same manner as in Example 5.

[Example 16]
The hydraulic resin of Example 16 under the same conditions as in Example 11 except that the same component (C) of ethylene oxide 6 mol adduct as in Example 12 was used and the blending ratio described in the Example 16 column of Table 6 was changed. A composition was obtained. This hydraulic resin composition was also subjected to various evaluation tests in the same manner as in Example 11. Further, the blending amounts of the cobalt octylate solution, dimethylaniline, and niper NS were adjusted to the blending ratios described in the column of Example 16 in Table 6. A resin concrete test was performed under the same conditions as in Example 15 except that the changes were made.

[Example 17]
The hydraulic resin of Example 17 under the same conditions as in Example 11 except that the same component (C) of ethylene oxide 6 mol adduct as in Example 12 was used and the blending ratio described in the Example 17 column of Table 6 was changed. A composition was obtained. For this hydraulic resin composition, various evaluation tests were conducted in the same manner as in Example 11. Further, for this hydraulic resin composition, the characteristics of the following glass-filled flake-containing composition (GF) were also measured.

  The characteristics of the composition containing glass flakes (GF) are 20% 120 degrees F / (FA-512MT) with respect to 100 parts by mass of the hydraulic resin composition blended in the composition of Example 17 above. ) After dissolving 3.0 parts by mass of paraffin wax (solid content of 0.6 parts by mass), 1.0 part by mass of 8% cobalt octylate solution, 0.2 parts by mass of dimethylaniline, Nyper NS (manufactured by NOF Corporation) Organic peroxide) 2.0 parts by mass was added and mixed, and then 25 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) was added to obtain a composition containing gala flakes. This compound was poured into a 40 × 40 × 160 mm mold to prepare a specimen for measuring compressive strength and bending strength. The tensile strength was prepared by pouring into a rod-shaped mold having a diameter of 2.5 cm.

[Example 18]
A hydraulic resin composition of Example 18 was obtained under the same conditions as in Example 11 except that the blending ratios described in the column of Example 18 in Table 6 were changed. The hydraulic resin composition was also subjected to various evaluation tests in the same manner as in Example 11. Further, the characteristics of the glass-containing flake-containing composition (GF) were also tested under the same conditions as in Example 17.

[Comparative Example 9]
Under the same conditions as in Comparative Example 1, a component (B) composed of an aromatic epoxy (meth) acrylate having an average molecular weight of 750 and an acid value of 15 KOH mg / g was obtained. Using this component (B), without using the component (A), a base composition was produced with the formulation described in the column of Comparative Example 9 in Table 6 below. (F), (G), and (F) were further blended with the blending described in the column to obtain a hydraulic resin composition of Comparative Example 9. Various evaluation tests were performed using the hydraulic resin composition under the same conditions as in Example 11.

[Comparative Example 10]
Without using the component (B), the hydraulic resin composition of Comparative Example 10 was produced with the formulation described in the column of Comparative Example 10 in Table 6 below. Various evaluation tests were performed using the hydraulic resin composition under the same conditions as in Example 11.

[Comparative Example 11 ]
Under the same conditions as in Comparative Example 4, an aromatic epoxy methacrylate having a number average molecular weight of about 1300 was produced and used as component (B). Using this component (B) and the same components (A), (B), (C), (D), and (E) as in Example 11 , comparison was made at the blending ratios described in the column for Comparative Example 11 in Table 6. The hydraulic resin composition of Example 11 was produced.

Various evaluation tests were performed using the hydraulic resin composition of Comparative Example 11 under the same conditions as in Example 11. As shown in Table 8, when the hydraulic resin composition of Comparative Example 11 was used, the concrete adhesion strength and the peeling strength between the concrete were low, and a primer, a base material adjusting material, and a surface protective material were laminated on the concrete. After the entire specimen was immersed in warm water of 80 ° C. for 25 days, countless bulges and peeling occurred between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the hot water (80 degreeC) immersion water absorption was as high as about twice that of the resin composition of the present invention.

[Comparative Example 12 ]
To 100 parts by mass of styrene type vinyl ester resin (Lipoxy R804 manufactured by Showa Denko KK), 1 part by mass of 8% cobalt octylate and 2 parts by mass of styrene vinyl ester resin curing agent (methyl ethyl ketone peroxide) manufactured by NOF A formulation was made. When each characteristic test was conducted under the same conditions as in Example 11 using this blend, the styrene volatilization amount was as extremely high as 80 g / m ² .

[Comparative Example 13 ]
A hydraulic resin composition of Comparative Example 13 was obtained under the same conditions as Comparative Example 11 except that the blending ratio was changed to that described in the Comparative Example 13 column of Table 6. Using this hydraulic resin composition, various evaluation tests were performed under the same conditions as in Example 11, and a resin concrete test was performed under the same conditions as in Example 15.

[Comparative Example 14 ]
The component (C) is changed to ethylene oxide 30 mol addition ethoxylated bisphenol A dimethacrylate (C) (Shin Nakamura Chemical Co., Ltd. BPE-1300), and the same aromatic epoxy methacrylate (number average molecular weight 1300) as in Comparative Example 11 is used. Furthermore, the hydraulic resin composition of the comparative example 14 was obtained on the same conditions as Example 11 except having changed the mixture ratio into the thing described in the comparative example 14 column of Table 6. Various evaluation tests were carried out under the same conditions as in Example 11 using this hydraulic resin composition, and the composition containing glass flakes under the same conditions as in Example 17 except that the amount of glass flakes was changed to 40 parts by mass. The properties of the product (GF) were also tested.

The compositions of Examples 11 to 18 and Comparative Examples 9 to 14 are shown in Table 6, and the evaluation test results are shown in Tables 7 to 8, respectively.

  In the table, * 1 indicates a composition containing glass flakes, and * 3 indicates an irritating odor of styrene monomer.

As described in Reference Example 1 above, the urethane methacrylate of component (A) is obtained by reacting until the absorption of the NCO group disappears in the infrared absorption spectrum. Therefore, the hydraulic resin composition using this component (A) The product and the lining material did not foam due to the urethane bond between the NCO group and moisture. In the non-styrene vinyl ester resin composition (components (B) to (E)) that does not contain the component (A), curing inhibition occurs due to moisture, so contact with water or contain water in the composition. However, the strength is inferior and chemical resistance and adhesiveness cannot be obtained. Such a non-styrene vinyl ester resin composition has (F) hydraulic cement, (G) water and (H) reduced cement water. Even when an agent was added and mixed with a peroxide, the above-mentioned drawbacks were not solved.

  In contrast, (A) urethane methacrylate and non-styrene vinyl ester resin composition (components (B) to (E)) are used in combination with the resin composition of the present invention, (F) hydraulic cement, (G) water. And the resin composition which added (H) and mixed with the peroxide formed the uniform hardened | cured material which does not have hardening inhibition, and sufficient intensity | strength, chemical-resistance, adhesiveness, etc. were obtained.

Claims (12)

(A) urethane (meth) acrylate having at least two (meth) acryloyl groups at the molecular ends;
(B) an epoxy (meth) acrylate comprising a reaction product of an aromatic epoxy resin and (meth) acrylic acid, having a number average molecular weight in the range of 500 to 1100 and an acid value of 10 KOHmg / g or less,
(C) ethoxylated bisphenol di (meth) acrylate having 2 to 10 moles of ethylene oxide added, and
(D) A monofunctional (meth) acrylate system having a group containing a cyclic hydrocarbon group having only one carbon-carbon double bond or one nitrogen atom in the ring as an alcohol residue having a molecular weight of 300 or less Containing monomers,
Moreover, (A), (B), (C) and the total 100 parts by mass of (D) having (E) phenyl (meth) acrylate - see including the Tomonoma -1～10 parts by weight
(A) Curable resin composition whose weight ratio (A) / (B) of urethane (meth) acrylate and (B) epoxy (meth) acrylate is 5/95 or more and 50/50 or less . For a total of 100 parts by mass of components (A), (B), (C) and (D),
(A) 10-50 parts by mass of urethane (meth) acrylate,
(B) 5-50 parts by mass of epoxy (meth) acrylate,
(C) 3-30 parts by mass of ethoxylated bisphenol di (meth) acrylate, and
(D) including 15 to 50 parts by mass of a monofunctional (meth) acrylate monomer,
Furthermore, the total of 100 parts by mass of (A), (B), (C) and (D) includes 1 to 10 parts by mass of (E) (meth) acrylate monomer having a phenyl group,
The weight ratio (A) / (B) of (A) urethane (meth) acrylate and (B) epoxy (meth) acrylate is 5/95 or more and 50/50 or less ,
2. The curability according to claim 1, wherein (C) the ethoxylated bisphenol di (meth) acrylate is a bifunctional (meth) acrylate monomer ethoxylated bisphenol A di (meth) acrylate. Resin composition. (A) the urethane (meth) acrylate, a polyalkylene glycol having a weight average molecular weight of 400 to 700, a polyisocyanate, a hydroxyl group one or more with (meth) in claim 1 or 2 is the polymerization product of acrylate monomer The curable resin composition described. (A) urethane (meth) acrylate having at least two (meth) acryloyl groups at the molecular ends;
(B) an epoxy (meth) acrylate comprising a reaction product of an aromatic epoxy resin and (meth) acrylic acid, having a number average molecular weight in the range of 500 to 1100 and an acid value of 10 KOHmg / g or less,
(C) ethoxylated bisphenol di (meth) acrylate having 2 to 10 moles of ethylene oxide added, and
(D) A monofunctional (meth) acrylate system having a group containing a cyclic hydrocarbon group having only one carbon-carbon double bond or one nitrogen atom in the ring as an alcohol residue having a molecular weight of 300 or less Containing monomers,
Furthermore, (A), (B), (C) and a curable resin composition comprising (E) phenyl group-containing (meth) acrylate monomer-1 to 10 parts by mass with respect to a total of 100 parts by mass of (A), (B), (C) and (D). Lining material including objects
Furthermore, the lining material containing hydraulic cement, a cement water reducing agent, and water . The lining material containing the curable resin composition of any one of Claims 1-3 . The lining material according to claim 4 or 5 , comprising 1 to 30 parts by mass of a thickener made of a thermoplastic resin powder with respect to 100 parts by mass of the curable resin composition. The lining material according to any one of claims 4 to 6, comprising 0.5 to 2.5 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the curable resin composition. The lining material according to any one of claims 4 to 7, comprising 5 to 50 parts by mass of a flaky inorganic filler with respect to 100 parts by mass of the curable resin composition. Furthermore, lining material according to any one of claims 4-8 containing an organic peroxide.   Furthermore, the lining material of Claim 9 which has a hydraulic cement and a cement water reducing agent.   Furthermore, the lining material of Claim 10 containing water. A curable resin composition according to any one of claims 1 to 4, comprising 100 to 600 parts by mass of a particulate or powdery inert inorganic material with respect to 100 parts by mass of the curable resin composition. Contains,
A concrete coating composition having an average particle size of the inorganic material in a range of 10 mm to 0.02 mm.