JP2007291179A - Curable resin composition, lining material and tubular lining material - Google Patents

Abstract

A curable resin composition having excellent low odor, water resistance, chemical resistance, durability, adhesion, and good thickening properties, and a tubular lining material using the composition.
SOLUTION: (A) 30 to 70% by mass of an unsaturated polyester having a number average molecular weight of 500 to 4000 and an acid value of 5 to 30 KOHmg / g, and (B) a monofunctional (meth) acrylate monomer 30 to 70 And (C) a curable resin composition comprising 1 to 30% by mass of a thickener made of thermoplastic resin powder, and the total of each mass% is 100% by mass; and this curability A tubular lining material using a resin composition.
[Selection] Figure 1

Description

  The present invention is suitable for use as a lining material for rehabilitation such as the inner surface of a tubular molded body, the inner surface of a square tube, the inner surface of a human hole, etc. of a sewerage treatment facility, the stability of thickening and thickening over time, high The present invention relates to a curable resin composition excellent in reactive light or thermal polymerization, chemical resistance, durability, adhesiveness, and hot water resistance, and a lining material and a tubular lining material containing the resin composition.

  Lining materials are used, for example, for rehabilitation of the inner surface of a tubular molded body, the inner surface of a square tube, the inner surface of a manhole, etc. in a sewerage treatment facility.

  As a curable resin composition used for the lining material as described above, an unsaturated polyester resin composition has been conventionally used. Recently, an unsaturated monobasic acid, particularly acrylic acid or methacrylic acid is added to an epoxy resin. Resin compositions containing epoxy (meth) acrylates obtained by reaction (generally vinyl ester resin compositions) are also used.

  Such known unsaturated polyester resin compositions and vinyl ester resin compositions generally use styrene as a copolymerizable monomer. However, this mixture of ester and styrene has a specific odor. For example, in an environment where the inner surface of a sewer pipe is used for rehabilitation of an existing pipeline or a concrete inner lining is used for a narrow underground structure, strict ventilation control is required. is there. As a countermeasure for the treatment, for example, a method of adsorbing the generated styrene with an activated carbon adsorption device is introduced. In addition, in relation to the sick house problem, styrene is subject to the setting of indoor concentration guideline values, and the PRTR system (Chemical Emission Control Management Promotion Act) designated as a Class I Designated Chemical Substance, and the system for disclosing the released and transferred amounts. And its management is necessary. In addition, regulations on styrene concentration in styrene-containing unsaturated polyester resins and vinyl ester resins are becoming stricter, and countermeasures are urgently required.

  Regarding low odor resin compositions that do not use or partially use styrene corresponding to the regulation of styrene concentration, there are many proposals, for example, Patent Document 1 (Japanese Patent Laid-Open No. 6-211952), Patent Document 2 (Japanese Patent Laid-Open Publication No. No. 8-283357), Patent Literature 3 (Japanese Patent Laid-Open No. 9-157337), Patent Literature 4 (Japanese Patent Laid-Open No. 11-12448), Patent Literature 5 (Japanese Patent Laid-Open No. 10-231453), Patent Literature 6 ( JP-A-11-255847), Patent Document 7 (JP-A 2001-240632), and Patent Document 8 (JP-A 2002-60282) disclose techniques relating to low odor. . Such patent documents describe compositions comprising epoxy acrylate and various low odor (meth) acrylate monomers.

  In addition, in order to repair existing pipes, tubular lining materials using thermosetting resins such as the unsaturated polyester resin composition and vinyl ester resin composition described above have been widely used, and gas pipes, water pipes, sewers are used. Liquid styrene type unsaturated polyester resin, styrene type vinyl ester resin or epoxy on the inside of the pipe for the purpose of reinforcing the strength of the pipe, preventing corrosion, leaking, flooding, or improving the flow rate of pipes such as manholes and sewers in facilities. A tubular lining material made of a fibrous cylindrical body impregnated with a resin is used. Such a tubular lining material is reversed and advanced by fluid pressure or the like, and the inverted tubular lining material is lined on the inner surface of an existing pipe by fluid pressure and pressed, and then the unsaturated polyester resin or vinyl ester resin of the lining material is heated or A method of forming a reinforced plastic tube by irradiating light and heating and curing the epoxy resin has been practiced.

  As the tubular lining material using the photopolymerizable resin composition that is cured by the above light irradiation, it is disclosed in Patent Document 9 (Japanese Patent Laid-Open No. 11-210981), Patent Document 10 (Japanese Patent Laid-Open No. 2003-33970), and the like. Has been. For example, Patent Document 9 describes a photocurable material containing an unsaturated polyester and / or vinyl ester resin (epoxy (meth) acrylate) and a bisacylphosphine oxide compound.

  Tubular lining material using epoxy (meth) acrylate (vinyl ester resin) containing (meth) acrylic monomer such as (low odor resin composition) is injected with heat source such as hot air, hot water, heated steam, etc. However, the curability is inferior to a tubular lining material using a styrene type unsaturated polyester resin or vinyl ester resin, and there is a problem that it takes a long time to cure and release water. On the other hand, a lining material using a styrene type unsaturated polyester resin or vinyl ester resin usually has a styrene vapor pressure of a polymerizable vinyl monomer contained in the resin when it is heated and cured by organic peroxide or photocured. Therefore, since it is volatilized in a relatively large amount and has an odor, the tube inner film after inversion is peeled off from the cured resin, and when it is pulled out, it causes air pollution due to volatilization in the tube and leakage from the manhole.

As a further required performance of the tubular lining material, a thickening property is required to maintain the film thickness. As such a thickening property, there is a gradual increase in viscosity at the initial stage of impregnation into fibrous materials such as glass fibers, felts and non-woven fabrics in the preparation of prepregs (sheets in which fibers are impregnated with resin). After the impregnation, it is required that the predetermined viscosity is reached in a short time and thereafter the viscosity change is small. Further, the preferred viscosity is a film in which the prepreg coating film is peeled well and the prepreg is uniform in the circumferential direction when the pipe-inserted prepreg is expanded in the range of the expanded air pressure of 0.4 to 0.5 kgf / cm ^2. This is a viscosity capable of ensuring a thickness, and therefore an excessively high viscosity is not appropriate. As an appropriate viscosity range after thickening of the resin composition containing a thickener, 500 to 3000 Pa · s is preferable. Below 500 Pa · s, the flowability of the prepreg is large, and the resin composition flows down in the circumferential direction of the tubular lining to become thicker, and the upper semicircular portion becomes thinner. It is difficult to ensure a uniform film thickness. If the viscosity of the resin composition is 3000 Pa · s or more, even if the air diameter expansion pressure is 1 kgf / cm ² or more, it is difficult to expand the prepreg, and the prepreg cannot be adhered to the rehabilitation (repair) pipeline. In addition, if there is a gap or attachment pipe port in the joint part of the pipe to be rehabilitated, if the diameter expansion pressure becomes large, the rehabilitation pipe is not constrained at the gap part and the attachment pipe port, so that the tubular lining material is damaged due to expansion. This is not preferable.

  In the low-odor photocurable resin composition or thermosetting resin composition that does not cause air pollution, magnesium oxide (Patent Document 9) is generally used as the thickener, and other fumed silicas. (Patent Documents 5 and 8), diisocyanate (Patent Document 9), and the like are also known.

  The low odor photocurable resin composition or thermosetting resin composition is generally composed of a low molecular weight, high viscosity oligomer and a low vapor pressure crosslinkable monomer. Compared with the resin composition and the styrene-type vinyl ester resin composition, since the crosslinkable monomer of the low odor resin does not contain a low-viscosity styrene monomer, the low odor resin is uniformly formed into a fibrous material. In order to impregnate, it is necessary to increase the addition rate of the crosslinkable monomer. As a result, since the content of free carboxyl groups in the resin composition is lowered, the intermolecular crosslink density of the composition is lowered, so that the thickening is slow. As a result, when the resin-impregnated tubular lining material is inserted into an existing pipeline and the diameter of the tubular lining material is increased, the resin composition may flow and the fibrous material may be impregnated unevenly. For this reason, the thickener which brings about an effective thickening effect is calculated | required.

Japanese Patent Laid-Open No. 6-211952 JP-A-8-283357 JP-A-9-157337 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 JP-A-11-210981 JP 2003-33970 A

  According to the study of the present inventor, magnesium oxide of the alkaline earth metal oxide usually used in styrene type unsaturated polyester resin and vinyl ester resin has intermolecular crosslinking between carboxyl groups liberated from the resin composition. However, since the crosslinking reaction is slow, the fibrous cylindrical body is impregnated with the resin composition, and usually 24 hours in a temperature environment of 40 ° C. or higher in order to promote thickening. A method is employed in which a predetermined viscosity range is reached by heating and aging for at least an hour. However, it has been found that it is difficult to reach the lower limit of the appropriate thickening range for the low odor resin composition.

  In addition, since the thickening effect of the thickener is insufficient, when supplemented by the addition of a filler such as calcium carbonate, the amount added is usually 100 parts by mass or more to 100 parts by mass of the resin composition, Since the amount of the filler becomes too large, it becomes difficult to impregnate the fibrous material.

  An object of the present invention is to provide a curable resin composition particularly useful for a lining material, which is excellent in low odor, water resistance, chemical resistance, durability, adhesion, and has a good thickening property. is there.

  Moreover, the objective of this invention is providing the lining material which has the said characteristic using the said curable resin composition.

  Furthermore, the objective of this invention is providing the tubular lining material which has the said characteristic using the said curable resin composition.

  As described above, since the low odor photocurable resin composition or thermosetting resin composition does not contain a low-viscosity styrene monomer, the fibrous material is uniformly impregnated with the low odor resin. In order to achieve this, it is necessary to increase the addition rate of the crosslinkable monomer, and the content of free carboxyl groups also decreases because the amount of resin decreases. In addition, when a low acid value non-styrene-containing unsaturated polyester resin having good properties such as water resistance is used, the content of free carboxyl groups and the content of hydroxyl groups in the composition are further reduced, so magnesium oxide, diisocyanate With conventional thickeners such as these, rapid thickening cannot be obtained.

As a result of intensive studies by the inventors on the above problems,
(A) 30-70% by weight of an unsaturated polyester having a number average molecular weight of 500-4000 and an acid value of 5-30 KOHmg / g, and (B) 30-70% by weight of a monofunctional (meth) acrylate monomer, and (C) A curable resin composition comprising 1 to 30% by mass of a thickener composed of a thermoplastic resin powder, wherein the total of each mass% is 100% by mass;
(A) 30-70% by mass of an unsaturated polyester having a number average molecular weight of 500-4000 and an acid value of 5-30 KOHmg / g, (B) 30-70% by mass of a monofunctional (meth) acrylate monomer, and ( D) 5 to 20% by mass of an alkoxylated bisphenol A dimethacrylate having an alkylene oxide addition mole number of 2 to 20, and (C) 1 to 30% by mass of a thickener made of a thermoplastic resin powder. Is a curable resin composition, wherein the alkylene oxide is preferably propylene oxide or ethylene oxide (particularly ethylene oxide). It is effective to suppress whitening of the cured product of the resin composition due to room temperature water or hot water immersion. In addition, the affinity and adhesive strength with the fibrous cylindrical body are remarkably excellent. ];
(A) 30-70% by weight of unsaturated polyester having a number average molecular weight in the range of 500-4000, (B) 30-70% by weight of monofunctional (meth) acrylate monomer, and (E) aromatic epoxy resin. 10 to 70% by mass of epoxy (meth) acrylate obtained by reaction of (meth) acrylic acid and 1 to 30% by mass of a thickener made of (C) thermoplastic resin powder, Curable resin composition characterized by being 100% by mass [In this curable resin composition, the chemical resistance (oxidation resistance) of the cured product is improved. And (A) 30-70% by weight of unsaturated polyester having a number average molecular weight in the range of 500-4000, (B) 30-70% by weight of monofunctional (meth) acrylate monomer, (D) addition of alkylene oxide 5 to 20% by mass of alkoxylated bisphenol A dimethacrylate having 2 to 20 moles, and 10 to 70% by mass of epoxy (meth) acrylate obtained by reaction of (E) aromatic epoxy resin and (meth) acrylic acid And (C) a curable resin composition comprising 1 to 30% by mass of a thickener comprising a thermoplastic resin powder, and the total of each mass% is 100% by mass;
The inventors have found that the above-mentioned problems can be solved.

  The number average molecular weight was measured using GPC method (gel permeation chromatography method). The molecular weight value is a polystyrene equivalent value.

Preferred embodiments of the curable resin composition of the present invention are as follows.
(1) (B) The monofunctional (meth) acrylate monomer is at least one (preferably one) carbon-carbon double bond and / or at least one (preferably one) in the ring as an alcohol residue. And a monofunctional (meth) acrylate monomer having a group containing a cyclic hydrocarbon group having a nitrogen atom. Low odor, water resistance, chemical resistance, durability and adhesion are further improved.
(2) (B) Monofunctional (meth) acrylate monomer having a group containing a cyclic hydrocarbon group having one carbon-carbon double bond in the ring as an alcohol residue And a monofunctional (meth) acrylate monomer having a group containing a hydrocarbon group having an aromatic group as an alcohol residue. Low odor, water resistance, chemical resistance, durability and adhesion are further improved.
(3) Further, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, It contains at least one (F) polyfunctional (meth) acrylic monomer selected from 1,6-hexanediol diacrylate and neopentyl glycol diacrylate. Water resistance, chemical resistance, durability, and adhesion are further improved. In order to demonstrate the viscosity adjustment function of the resin composition, especially when used in combination with monofunctional (meth) acrylate monomers, the workability of unsaturated polyester, impregnation into fibrous cylinders, etc. The viscosity at 25 ° C. of the polymerizable (meth) acrylic monomer is preferably 10 mPa · s or less.
(4) (B) The monofunctional (meth) acrylic monomer has a molecular weight of 200 or more, a viscosity at 25 ° C. of 100 mPa · s or less, and a vapor pressure of 0.5 mmHg or less. It is easy to keep the odor low.
(5) (B) The monofunctional (meth) acrylic monomer is a group in which the alcohol residue of (meth) acrylic acid is bonded to the cyclic hydrocarbon group and the oxyalkylene group. It is particularly excellent in curability.
(6) (B) The monofunctional (meth) acrylic monomer is selected from dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, and pentamethylpiperidyl methacrylate. At least one monomer. In particular, curability, adhesion strength stability, and weight change rate stability are excellent.
(7) (A) Unsaturated polyester has _Mw / _Mn of 4.0 or less. It is preferable because a viscosity that is easy to handle is easily obtained.
(8) The thermoplastic resin powder (C) has an average particle size of 0.1 to 5.0 μm, particularly 0.2 to 3.0 μm. As the thermoplastic resin, an acrylic resin is preferable.

  Moreover, this invention exists also in the lining material containing a curable resin composition.

Furthermore, the present invention provides an inner surface and / or an outer surface of a tubular curable composite material obtained by impregnating a fiber layer cylindrical body with a photocurable resin composition containing the curable resin composition for a lining material and a photopolymerization initiator. A tubular lining material formed by impregnating a fibrous layer cylindrical body with a tubular lining material coated with at least one tube; and a thermosetting resin composition containing the curable resin composition for a lining material and a thermal polymerization initiator. A tubular lining material formed by coating the inner surface and / or outer surface of the curable composite material with at least one tube;
There is also.

  In the tubular lining material, an alkaline earth metal oxide and / or hydroxide and / or metal alkoxide is added to 0.1 part by mass of the curable resin composition for lining material and 100 parts by mass of the curable resin composition. It is preferable to contain 3-10 mass parts. Use of an appropriate amount is particularly effective when moderate thickening in a short time is required.

  Moreover, it is preferable to contain 0.3-10 mass parts of 1 or more types of compounds which have an isocyanate group with respect to 100 mass parts of curable resin composition for lining materials, and curable resin composition. Use of an appropriate amount is particularly effective when moderate thickening in a short time is required.

  The curable resin composition of the present invention uses a specific low acid value unsaturated polyester, a polymerizable monofunctional (meth) acrylic monomer, and a thickener for thermoplastic resin powder in a specific composition ratio. . Thereby, there is no styrene volatilization, thickening is possible in a short time, and workability is good. Furthermore, the curability and the surface drying property are good, and the physical properties of the cast plate and the laminated plate, the reactivity of photopolymerization and thermal polymerization are all superior to those of the existing styrene-type vinyl ester resin cured products.

  In particular, when the unsaturated polyester and a specific polymerizable monofunctional (meth) acrylic monomer having high reactivity and low volatility are used as the polymerizable monofunctional monomer, the above thickening, curability and surface drying properties, light The reactivity of polymerization and thermal polymerization becomes more excellent.

  In addition, the lining material of the present invention particularly suitable for a tubular body does not generate styrene odor before and after curing, does not cause contamination of the surrounding environment, can be thickened in a short time, and has good workability. In addition, the fibrous cylindrical body impregnated with the resin composition does not generate wrinkles due to swelling, deterioration, or softening of the tube due to styrene, even if the inner and outer tubes covered by this are one layer. Since thermal polymerization and photopolymerization curability function effectively, there is no need to use a two-layer tube as in the prior art.

  In the present invention, the unsaturated polyester that is one of the essential components of the curable resin composition is any known one as long as it has a number average molecular weight of 500 to 4000 and an acid value of 5 to 30 KOHmg / g. Unsaturated polyesters can be used. Unsaturated polyesters obtained by esterification reaction of α, β-unsaturated carboxylic acid and polyhydric alcohol, followed by deglycolization reaction are generally used. A saturated carboxylic acid may be included in addition to the α, β-unsaturated carboxylic acid.

  Usually, the ortho system can be esterified after the one-stage reaction, the iso system can be converted into the two-stage reaction, and the tele system can be esterified after the transesterification reaction. The reaction temperature during esterification is preferably in the range of 190 to 220 ° C.

  In order to obtain a highly reactive ester, 200 ° C. or lower is desirable. While flowing nitrogen gas, esterification can be carried out by a conventional method.

  The deglycolization reaction is performed by adding a catalyst when the acid value in the esterification reaction is 70 KOH mg / g or less, preferably 40 KOH mg / g or less. The deglycolization reaction is preferably performed in the presence of a catalyst at a temperature of 180 to 220 ° C. for 2 to 16 hours at a pressure of 5 torr or less. The acid value of the obtained unsaturated polyester is 5 to 30 KOHmg / g, and 15 to 30 KOHmg / g is particularly preferable. Since the acid value is low, thickening with thermoplastic resin powder is particularly effective. The unsaturated polyester obtained has a hydroxyl value of 10 to 200 KOHmg / g, more preferably 15 to 170 KOHmg / g, and particularly preferably 15 to 30 KOHmg / g. As in the unsaturated polyester of the present invention, an unsaturated polyester having a low acid value and further having a low hydroxyl group has a stable thickening behavior, and such an unsaturated polyester is monofunctional (meth) acrylic. When combined with a monomer, stable thickening properties can be obtained, which is advantageous.

  Examples of the α, β-unsaturated carboxylic acid include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, and dimethyl esters thereof. These α, β-unsaturated carboxylic acids may be used alone or in combination of two or more. Examples of saturated carboxylic acids that can be used include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hetic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, adipic acid, and sebacic acid. These saturated carboxylic acids may be used alone or in combination of two or more.

  On the other hand, as the polyhydric alcohol, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3- Propanediol, 1,6-hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, Examples include diols such as alkylene oxide adducts of hydrogenated bisphenol A, triols such as trimethylolpropane, and tetraols such as pentaerythritol. These polyhydric alcohols may be used alone or in combination of two or more.

  Further, dicyclopentadiene-based unsaturated polyester obtained by adding dicyclopentadiene and reacting with the α, β-unsaturated carboxylic acid, saturated carboxylic acid and polyhydric alcohol can also be used.

  Moreover, it reacts with the above α, β-unsaturated carboxylic acid and polyhydric alcohol as a main raw material, a glycol decomposition product obtained by reacting recovered polyethylene terephthalate (hereinafter abbreviated as PET) and polyhydric alcohol at a high temperature. The PET unsaturated polyester obtained in this way can also be used as the unsaturated polyester of the present invention.

  The unsaturated polyester of the present invention has a number average molecular weight (Mn) in the range of 500 to 4000, preferably in the range of 500 to 3000, and particularly preferably in the range of 1000 to 2000. When the number average molecular weight exceeds 4000, the viscosity of the unsaturated polyester itself is undesirably high. On the other hand, if it is less than 500, an unreacted monomer is present in the unsaturated polyester, and the physical properties are deteriorated. Further, by using an unsaturated polyester having a number average molecular weight in the above preferred range, a polyester having particularly excellent curability, drying properties and mechanical properties can be obtained. In the present invention, as the unsaturated polyester, the acid value is relatively low, and a relatively low molecular weight is used as described above. The composition of the present invention containing such a resin is particularly suitable for thickening with a thermoplastic resin powder.

Further, the molecular weight distribution (weight average molecular weight (M _w ) / number average molecular weight (M _n )) of the unsaturated polyester is preferably 4 or less. If it exceeds 4, even if a thickener is added, the initial thickening is large and the impregnation property into the fibrous cylindrical body is deteriorated, which is not preferable. Particularly preferred is 3.5 or less.

  The amount of the (A) unsaturated polyester used is an essential component constituting the resin composition used in the present invention (A) to (E) {that is, (A), (B) and (C) (( In the case of using D) and / or (E), the total amount including them)} is in the range of 30 to 70% by mass (preferably 35 to 65% by mass).

  In the present invention, (B) a monofunctional (meth) acrylate monomer is used as the polymerizable monomer. (B) As the monofunctional (meth) acrylate monomer, known monomers can be used, but at least one carbon carbon double bond or nitrogen atom (particularly one) in the ring as an alcohol residue. It is preferable to use a monofunctional (meth) acrylate monomer having a group containing a group containing a cyclic hydrocarbon group. Further, in the monofunctional (meth) acrylic monomer, the alcohol residue of (meth) acrylic acid is particularly preferably a group in which the cyclic hydrocarbon group and the oxyalkylene group are bonded.

  Examples of usable monomers of the monofunctional (meth) acrylic monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and t-butyl. Acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl Examples include methacrylate and n-octyl methacrylate.

  Furthermore, as a preferable example of a monofunctional (meth) acrylic monomer,

  Dicyclopentenyloxyethyl acrylate

  Dicyclopentenyloxyethyl methacrylate

  Dicyclopentanyl acrylate

  Dicyclopentanyl methacrylate

  Dicyclopentenyl acrylate

  Dicyclopentenyl methacrylate

  Pentamethylpiperidyl methacrylate

And pentamethylpiperidyl acrylate

等を挙げることができる。さらに好ましいモノマーとして、ベンジルアクリレート、ベンジルメタクリレート、フェニルアクリレート、フェニルメタクリレート等の芳香族（メタ）アクリレートも挙げることができる。これらは単独使用、又は２種類以上を併用してもよい。芳香族（メタ）アクリレートは、アルコール残基が置換基（好ましくは低級アルキル基）を有していても良いフェニル又はベンジル基（特に置換基の無いフェニル又はベンジル基）が好ましい。

Etc. More preferable monomers include aromatic (meth) acrylates such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, and phenyl methacrylate. These may be used alone or in combination of two or more. The aromatic (meth) acrylate is preferably a phenyl or benzyl group (particularly an unsubstituted phenyl or benzyl group) in which an alcohol residue may have a substituent (preferably a lower alkyl group).

  (B) A monofunctional (meth) acrylate monomer having a group containing a cyclic hydrocarbon group having one carbon-carbon double bond in the ring as the alcohol residue as the monofunctional (meth) acrylate monomer And a monofunctional (meth) acrylate monomer having a group containing a hydrocarbon group having an aromatic group as an alcohol residue are also preferable because a viscosity that is easy to handle is easily obtained. The mass ratio of the former to the latter (the former: the latter) is generally 7: 3 to 3: 7, and 6: 4 to 4: 6 is particularly preferable.

  Of these, dicyclopentenyloxyethyl methacrylate and dicyclopentenyloxyethyl acrylate are preferably used in the present invention in consideration of low odor, reactivity, and properties of the cured product. When the tubular lining material is cured by light irradiation, the terminal acryloyl group-type dicyclopentenyloxyethyl acrylate is preferable because the polymerization rate is faster than that of the terminal methacrylate, but two types may be used in combination.

  The (B) monofunctional (meth) acrylic monomer of the present invention is also preferably a monomer having a molecular weight of 200 or more, a viscosity at 25 ° C. of 100 mPa · s or less, and a vapor pressure of 0.5 mmHg or less. Such monomers are generally low in volatility and have little environmental pollution.

  In addition to the polymerizable monomer (B) in the present invention, (F) a polyfunctional (meth) acrylate can be used as necessary. Preferred examples of the polyfunctional (meth) acrylate include neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6- Examples include hexanediol dimethacrylate, 1,6-hexanediol diacrylate, and neopentyl glycol diacrylate. (F) The polyfunctional (meth) acrylate is preferably used in an amount of 20 to 150 parts by mass, particularly 20 to 120 parts by mass with respect to 100 parts by mass of the polymerizable monomer (B).

  In order to demonstrate the function of adjusting the viscosity of the resin composition, especially when used in combination with monofunctional (meth) acrylate monomers, workability of unsaturated polyester, impregnation into fibrous tubular bodies, etc. It is preferable that the 25 degreeC viscosity of a property (meth) acrylic-type monomer is 10 mPa * s or less. Furthermore, it is preferable that the molecular weight is 300 or less and the vapor pressure is 0.5 mmHg or less.

  The polyfunctional (meth) acrylic monomer is preferably a low-viscosity monomer compared to the monofunctional (meth) acrylic monomer. By using the monofunctional monomer and the polyfunctional monomer in combination, Viscosity can be adjusted at almost the same addition rate as styrene dilution, and both photocurability and thermosetting are good, which is preferable.

  The use amount of the (B) monofunctional (meth) acrylic monomer (if necessary, a polyfunctional (meth) acrylate monomer) is an essential component constituting the resin composition used in the present invention (A) to ( E) in the range of 30 to 70% by mass (preferably (A) to (C) (when (D) and / or (E) is used)) If it is less than 30% by weight, the cured product of the resin composition is inferior in surface finger dryness, the resin composition has a high viscosity, and is inferior in workability. Moreover, when it exceeds 70 mass%, a swelling will generate | occur | produce on the surface of hardened | cured material in high temperature water immersion, and it will be inferior to durability. Therefore, it is necessary to use within the above range. The (B) monofunctional (meth) acrylic monomer is preferably used in an amount of 50 to 120% by mass, particularly 65 to 100% by mass, based on the (A) unsaturated polyester resin.

  (C) which is an essential component constituting the curable resin composition used in the present invention uses a known thickening agent for thermoplastic resin powder. The amount of the thermoplastic resin powder used is the total amount of (A) to (E) {ie (A) to (C) (when (D) and / or (E) is used, the whole including them)} It is 1-30 mass% with respect to it, Preferably it is 1-10 mass%.

  Known thermoplastic resin powders include polystyrene powder, polyolefin resin powder (eg, polyethylene resin powder), polyvinyl chloride resin powder, polyurethane resin powder, acrylic resin powder, and the like. The thermoplastic resin powder of the acrylic resin mentioned later is preferable.

  The average particle diameter of the thermoplastic resin powder is generally 0.1 to 5.0 μm, preferably 0.2 to 3.0 μm. When the average particle size is less than 0.1 μm, the monofunctional (meth) acrylic monomer or polyfunctional (meth) acrylic monomer as the component (B) has a high absorption rate at room temperature and has a viscosity of There is a possibility that impregnation into the fibrous cylindrical body may not be easy because it becomes too high. When the average particle size exceeds 5.0 μm, the absorption rate of the monofunctional (meth) acrylic monomer (B) and / or the polyfunctional (meth) acrylic monomer is slow, and the thickening is slowed. The weight average degree of polymerization is 1,000 to 150,000. When the weight average degree of polymerization exceeds 150,000, the absorption rate of the monofunctional (meth) acrylic monomer (B) and / or the polyfunctional (meth) acrylic monomer becomes slow, and the viscosity increases even after a long time. Granting is difficult. In addition, when the molecular weight is less than 1,000, the absorption rate of the monofunctional (meth) acrylic monomer and / or the polyfunctional (meth) acrylic monomer is high and the viscosity is rapidly increased, so that the fibrous material is impregnated. It becomes ununiform, and the mechanical strength of the cured prepreg is low, and the chemical resistance is remarkably lowered, which is not preferable. In addition, when the thermoplastic resin powder is copolymerized with a crosslinkable monomer, if the crosslinking degree is too high, it tends to take a long time to form a prepreg sheet having an appropriate viscosity. It is preferable that the insoluble gel component when the plastic resin powder is dissolved in a solvent is 50% by weight or less.

  About the manufacturing method of the thermoplastic resin powder which is (C) component, it is shown by well-known literature, for example, Unexamined-Japanese-Patent No. 9-188770. It is roughly classified into a homogeneous component polymer (homopolymer), a copolymer of two or more monomers, and a core / shell structure. The resin composition in which (C) is added to (A) to (E) {i.e., (A) to (C) (the whole containing (D) and / or (E))} is adjusted. Immediately after the addition, the viscosity is low and the viscosity increases rapidly after the addition of the fibrous material. Thereafter, the viscosity shows stability over time.

  The thermoplastic resin powder absorbs a monofunctional (meth) acrylic monomer and / or a polyfunctional (meth) acrylic monomer as the thermoplastic resin powder, as shown in known JP-A-9-174781. Is not particularly limited as long as it swells, and has at least one monomer unit selected from acrylic acid ester, methacrylic acid ester and aromatic vinyl compound in an amount of 50% by weight or more, and carboxyl It is preferably an acrylic resin thermoplastic resin powder having 1 to 20% by weight of a group or epoxy group-containing monomer unit.

  Monomers used for the production of thermoplastic resin powders include (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, sec-butyl acrylate. , T-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, etc .; and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl Examples thereof include methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate and the like. Of these monomers, methyl methacrylate is particularly preferred. 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, Examples thereof include vinyl toluene and isobutyl styrene. These monomers can be used alone or in combination of two or more. If the content of the monomer unit of the acrylic ester, methacrylic 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 as component (C) may contain other monomer units copolymerizable with the above-mentioned monomers. Examples of other copolymerizable monomers include acrylonitrile. Vinyl cyanides such as methacrylonitrile; vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl oleate, vinyl oleate, vinyl benzoate; acrylic acid, methacrylic acid, 2-ethylpropionic acid Unsaturated dicarboxylic acids such as crotonic acid and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, citraconic acid and chloromaleic acid; unsaturated such as monomethyl maleate, monoethyl maleate and monobutyl itaconate Monoesters of dicarboxylic acids; butagen, isoprene, 1,3-pentagen, cyclopentadiene Conjugated diene compound and the like; 1,4-hexane, can be mentioned non-conjugated diene compounds such as dicyclopentadiene. 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 unsaturated polyester resin composition, the polymer constituting the thermoplastic resin powder is appropriately crosslinked. be able to. 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-aminopyrrole (meth) acrylate, N-2-aminoethyl (meth) acrylamide, N-3-aminopropyl (meth) acrylamide, ethylene group number 1 to 14 monomers such as polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triallyl trimellitate, diallyl phthalate, allyl glycidyl ether, triallyl isocyanurate. The amount of the crosslinkable monomer 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. Other copolymerizable monomers can be used alone, or two or more can be used in combination.

  The production method is not particularly limited, and a method conventionally used for producing fine resin powder such as polymethyl methacrylate (Japanese Patent Laid-Open No. 9-188770), for example, fine suspension polymerization method, emulsion polymerization method, seeding An 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 alkylaryl sulfuric acid ester salts; and anionic interfaces such as sodium dodecyl diphenyl ether disulfonate Activants; sorbitan esters such as sorbitan monooleate and polyoxyethylene sorbitan monostearate; Can be cited cetylpyridinium chloride, a cationic surfactant, such as such as cationic such as cetyltrimethylammonium bromide; nonionic surfactants such as polyoxyethylene alkyl ethers. Examples of the dispersant include polyvinyl alcohol, methyl cellulose, and polyvinyl pyrrolidone. These surfactants and dispersants may be used alone or in combination of two or more. The amount of use can be suitably selected in the range of 0.05 to 5 parts by mass, preferably 0.2 to 4 parts by mass, per 100 parts by mass of the monomer used.

  The thermoplastic resin powder as the component (C) is a homogenous component polymer (homopolymer) or a copolymer of two or more monomers as shown in known literature, for example, JP-A-9-188770. In the present invention, the thermoplastic resin powder as the component (C) has a carboxyl group-containing monomer unit or an epoxy group-containing monomer unit in an amount of 1 to 20% by weight. It can be set as the core / shell type structure which has the polymer to contain in a shell layer. When the core component is a (meth) acrylic acid ester-based polymer and / or a gen-based 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 are It is preferable because it greatly improves.

  The curable resin composition of the present invention preferably further comprises (D) an alkoxylated bisphenol A dimethacrylate having 2 to 20 moles of alkylene oxide added. As said alkoxylated bisphenol A dimethacrylate, the thing of the ester compound of the bihydric alcohol which added the alkylene oxide to bisphenol A and / or bisphenol F, and methacrylic acid can be mentioned. For bisphenol, bisphenol A is preferred. The alkylene oxide is preferably propylene oxide or ethylene oxide, and particularly preferably ethylene oxide. Excellent reactivity.

  When the number of moles of alkylene oxide added to the alkoxylated bisphenol A dimethacrylate of (D) exceeds 20, the crosslinking density decreases, thereby reducing the reactivity of the curable resin composition, the water resistance of the cured product, particularly at room temperature. Increase in weight change rate of water and hot water immersion, affinity with fibrous cylindrical body, and adhesive strength are lowered, and use in a liquid phase environment tends to be unsuitable. On the other hand, if the number of moles of alkylene oxide added is less than 2, it is not preferable because the viscosity of the resin composition becomes high and the work becomes difficult. For example, ethoxylated bisphenol A dimethacrylate is a known method described in JP-A-7-268079. First, a nucleated polyol obtained by adding ethylene oxide to bisphenol A and an epihalohydrin are ether-reacted to form an alkylene oxide-added bisphenol A. Diglycidyl is obtained and then obtained by reacting it with methacrylic acid using an esterification catalyst.

  By using the alkylene oxide-added ethoxylated bisphenol A dimethacrylate represented by (D), the reactivity of the resin composition, the weight change rate stabilized by water immersion and hot water immersion of the curable resin composition, and the fiber tube Affinity and durability with the shape are improved, which is preferable. (D) The content of alkylene oxide-added alkoxylated bisphenol A dimethacrylate is the total amount of (A) to (E) constituting the curable resin composition of the present invention {ie, (A) to (C) (( D) and / or (E) in the case of using the whole))} in the range of 5 to 20% by mass (especially 5 to 15% by mass) (the total of each mass is 100% by mass) Is). That is, if it is less than 5% by mass, the surface of the cured product of the resulting curable resin composition is likely to whiten when immersed in room temperature water and warm water, and if it is 20% by mass or more, the cured curable resin composition is cured when immersed in water and warm water. This is not preferable because blisters are easily generated in the object.

  Moreover, it is preferable that the curable resin composition of this invention contains (E) epoxy (meth) acrylate further. The content is a total amount of (A) to (E) which is an essential component constituting the curable resin composition of the present invention {ie, (A) to (C) ((D) and / or (E). Is preferably in the range of 10 to 70% by mass (particularly in the range of 20 to 50% by mass) (the total of each mass is 100% by mass). If it is less than 10% by mass, the resulting cured product may be inferior in chemical resistance and oxidation resistance. If it exceeds 70% by mass, the viscosity tends to increase and the viscosity of the resin composition increases. The uniform impregnation property and workability as a lining material may be inferior.

  The aromatic epoxy (meth) acrylate of the component (E) of the resin composition of the present invention is obtained by a reaction between an aromatic epoxy resin and an unsaturated monobasic acid such as (meth) acrylic acid. Examples of the aromatic epoxy resin (that is, an epoxy resin having an aromatic ring in the molecule) used as a raw material for the aromatic epoxy (meth) acrylate include a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an alkyl. Novolac type epoxy resins such as phenol type epoxy resin, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol type epoxy resin, resorcin type epoxy resin N-glycidylamine type epoxy resin, brominated bisphenol A type epoxy resin, and the like.

  These epoxy resins may be used alone or in combination of two or more. Of these, bisphenol A type epoxy resins are more preferred because they provide balanced properties to concrete-coated curable resin compositions and cured lining materials such as tubes.

  As described above, the aromatic epoxy (meth) acrylate is obtained from a normal reaction between the aromatic epoxy resin and an unsaturated monobasic acid such as (meth) acrylic acid. The unsaturated monobasic acid to be reacted with the epoxy resin is acrylic acid or methacrylic acid, but other unsaturated monobasic acids such as crotonic acid, sorbitan acid, cinnamic acid, acrylic acid dimer, monomethyl malate, monomethyl fumarate, A small amount of monocyclohexyl fumarate or sorbic acid can be used in combination. These acids are used alone or in combination of two or more. In addition, as a photopolymerization resin composition, it is common to use acrylic acid from the polymerization rate for the unsaturated monobasic acid used as one of the reaction products of epoxy (meth) acrylate.

  The reaction ratio between the aromatic epoxy resin and (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 as an esterification catalyst, tertiary amines such as triethylamine and dimethylaniline, quaternary ammonium salts such as trimethylbenzylammonium chloride, triethylbenzylammonium chloride and pyridinium chloride, water Inorganic salts such as lithium oxide and lithium chloride are used. A polymerization inhibitor is used as necessary, and examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone, benzoquinones such as benzoquinone and methyl-p-benzoquinone, catechols such as t-butylcatechol, 2,6- Examples thereof include phenols such as di-t-butyl-4-methylphenol and 4-methoxyphenol, and phenothiazine.

  Moreover, the curable resin composition of this invention contains (D) component and can further contain (E) epoxy (meth) acrylate as mentioned above. Alternatively, the component (E) may be included without including the component (D).

  In the curable resin composition of the present invention, the thermoplastic resin powder is used as a thickener, but secondary (in an amount of 50% by mass or less of the thermoplastic resin powder) the following alkaline earth metal: These oxides, hydroxides, metal alkoxides, and compounds having an isocyanate group may be used.

  Examples of alkaline earth metal oxides, hydroxides, and metal alkoxides include, for example, alkaline earth metal magnesium oxide, magnesium hydroxide, potassium oxide, calcium hydroxide, and metal alkoxides, such as aluminum isopropylate. -Methyl acetoacetate aluminum dibutyrate, Methyl ethyl acetoacetate aluminum dibutylate, Propyl acetoacetate aluminum diisopropylate, Ethyl acetoacetate aluminum diethoxyethylate , Ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate) alone or in an appropriate mixture are used in combination with an alkaline earth metal.

  In addition, the tubular lining material of the present invention utilizes the thickening of aggregate formation due to the coordinate bond between the acid group of the unsaturated polyester molecule terminal and the alkaline earth metal such as magnesium oxide, which is an essential component of the curable resin composition. And it can mix with the said curable resin composition and can exhibit the thickening effect.

  Therefore, unsaturated polyester, monofunctional (meth) acrylic monomer and / or polyfunctional (meth) acrylic monomer and ethoxylated bisphenol A di (meth) acrylic which are one of the components of the curable resin composition Mixtures composed of monomer and thickener (thermoplastic resin powder and the above oxides) and mixtures composed of epoxidized (meth) acrylate with the above mixture are both initially thickened and impregnated into fibrous cylindrical bodies. And may be used to adjust the final viscosity of the prepreg. Due to thickening, the tubular lining material is inserted into the existing pipe line, and even if it is brought into close contact with the inner wall of the pipe with compressed air or water, the thickening prepreg does not change in thickness and does not flow when inserted. A tube having a uniform thickness is formed.

  When the alkaline earth metal oxide and / or hydroxide and / or metal alkoxide is also used as a thickener added to the curable resin composition in the present invention, the amount used is the resin composition. 0.3 with respect to the total amount of constituent components (A) to (E) {that is, (A) to (C) (the whole including (D) and / or (E) when they are used)} 10 mass% is contained. If it is less than 0.3% by mass, the combined effect of the thermoplastic resin powder with the thickener cannot be exhibited. On the other hand, when the content is 10% by mass or more, the change in viscosity with time is remarkable, and it is practically impossible to expand the diameter of the prepreg.

  You may make it thicken by making an isocyanate group react with the hydroxyl group in the molecular structure of (A). Compounds having an isocyanate group include 4,4-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate and its isomer or a mixture of isomers, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogen Examples thereof include polyisocyanates such as xylylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate, and one or more of them can be used. Of the polyisotoanates, diisocyanates are preferably used. In order to promote the reaction between an isocyanate group and a hydroxyl group, it is also effective to combine a compound having an isocyanate group with one or more selected from an organic tin compound, a tertiary amine, and an ammonium salt. Known urethanization catalysts such as onium salts, lithium halides, metal acetylacetonates, titanate compounds such as known organotin compounds, tertiary amines, and organic quaternary ammonium halides can be used in combination.

  When a compound having an isocyanate group is used in combination as a thickener added to the curable resin composition in the present invention, the amount used is the total amount of the components (A) to (E) constituting the resin composition { That is, 0.3-10 mass% is contained with respect to (A)-(C) (when (D) and / or (E) are used, the whole containing them)}. If it is less than 0.3% by mass, the combined effect of the thermoplastic resin powder with the thickener cannot be exhibited. On the other hand, when the content is 10% by mass or more, the change in viscosity with time is remarkable, and it is practically impossible to expand the diameter of the prepreg.

  Examples of the fibrous cylindrical body used in the tubular lining material of the present invention include inorganic reinforcing materials such as glass fibers, carbon fibers, and metal fibers; or olefins such as aramid fibers, polyester fibers, vinyl ester fibers, polyethylene, and polypropylene. Fibers: Polyolefin, polyester, polyamide, aromatic resins, etc., known spunbond and melt flow nonwoven fabrics; Reinforcement material consisting of long needle punch felts such as polyester, polyamide, polypropylene Can be mentioned. In general, a glass fiber fabric, felt or the like is used as a cylindrical body. For the production of the cylindrical body, for example, the methods described in JP-A-58-33098 and JP-A-2-221245 can be used.

  The curable composition of the present invention is used as a lining material, and as a material of a tube covered with this curable composition and a tubular curable composite material obtained from the above fibrous cylindrical body, known polyurethane rubber, polychlorinated Films of vinyl, polyethylene, polypropylene, polyamide, polyethylene terephthalate, etc. are known and can be used. Such materials are described in, for example, Japanese Patent Publication No. 58-9317, Japanese Patent Publication No. 1-15374, and Japanese Patent Application Laid-Open No. 4-5020. However, when the styrene monomer contained in the styrenic unsaturated polyester resin or styrenic vinyl ester resin comes into contact with the urethane elastomer film, the film swells, deteriorates, softens, and wrinkles occur on the surface of the cured composite material. It is not preferable because sometimes fluidity is hindered. In addition, both thermal curing by press-fitting heated water and hot air and photocuring by photopolymerization generate a temperature rise due to reaction heat in the composite material, so films with low heat resistance such as polyethylene, polypropylene, and polyvinyl chloride are softened. Since the melting occurs and adheres to the surface of the cured composite material, it is difficult to peel the film from the composite material. Since the curable resin composition used in the present invention does not contain a styrene monomer having a high vapor pressure or contains only a small amount, it has the same tensile strength and tear strength as those of polyamide and a high elongation urethane elastomer film. Even when the cured composite material comes into contact, the phenomenon of swelling, alteration and softening of the film does not occur. For this reason, even at least one tube on the inner and outer surfaces, for example, a configuration of a urethane elastomer film alone can be used because it is not affected by styrene from the resin composition at all. In the case of a material having high heat resistance such as a polyamide film or a polyethylene terephthalate film or a urethane elastomer film, the temperature rise due to reaction heat of the curable composite material used in the present invention and hot water or warm air (45 to 80 ° C.) are heated. However, due to the high heat resistance of the film, there is no generation of wrinkles on the surface of the cured composite material due to film swelling, alteration, and softening, and the tensile strength exceeds that of polyolefin.

  The film thickness of the tube composed of one layer on the inner and outer surfaces depends on the tube diameter of the tubular lining material. However, when the tube diameter is 400 mm or less, it is preferable that the maximum film thickness is 300 μm in consideration of thermal conductivity by thermosetting and permeability by photocuring. Maintains the strength to withstand peeling of the film (tube) from the tubular lining material (curable composite material) and the strength to withstand the tension of the uncured tubular lining material when laying the tubular lining material in the pipeline. There is a need to. The curable resin composition used in the present invention is an essential component, and at least one tube holding a curable composite material impregnated into a fibrous cylindrical body is a conventional one that uses styrene as a copolymerizable monomer. The problem of using at least a two-layer tube derived from the necessary function of the tube holding the unsaturated polyester resin and vinyl ester resin impregnated fibers has been eliminated. The tube used in the present invention is preferably a tube made of a film of urethane elastomer, polyamide, polyethylene terephthalate, polyester elastomer or the like for the above reasons. The inner and outer surface of the tube is composed of a single layer, and the retention of the curable composite material of the present invention and the function of the tube can be achieved. Good. The compounding method may be either a laminate or a method in which each film is inserted.

  FIG. 1 shows an example of an existing pipe 5 in which a tubular lining material 1 covered with at least one layer of a tube is provided on the inner surface and / or outer surface of the curable resin composition-impregnated fiber layer cylindrical body of the present invention. .

  The tubular lining material 1 of the present invention includes a fiber layer tubular body 3 in which a fiber layer tubular body composed of reinforcing fibers such as glass fiber and polyester fiber is impregnated with the uncured cured resin composition of the present invention, The outer peripheral surface is composed of an inner coating 2 and an outer coating 4 sandwiching the fiber layer cylindrical body 3 with a transparent plastic film such as polyurethane. The tubular lining material 1 of the present invention is integrated with the fiber layer cylindrical body 3, the inner coating 2 and the outer coating 4 with a good appearance without wrinkles and high tensile strength as described above. The lining material of the present invention containing the cured resin composition can be advantageously used for producing the tubular lining material.

  The tubular lining material of the present invention is obtained by impregnating a tubular tubular lining material in which a fibrous tubular body is impregnated with a thermosetting resin composition or a photocurable resin composition and encapsulated by two films on the outer side and the inner side. Manufactured. Regarding the kind of the film, polyurethane rubber is cited as the inner film described in Japanese Patent Publication No. 1-15374. The inner and outer films may be of the same type or different types, as long as the flexibility and flexibility of maintaining the flexibility and flexibility of the tube lining material before curing are not inhibited. As a device for coating the tubular lining material of the tubular lining material of the present invention, for example, the methods described in US Pat. No. 4,668,0066, Japanese Patent Publication No. 1-416670, Japanese Patent No. 3413633, and the like can be used. That is, in a state where the tubular tubular lining material is in close contact with the existing tubular body wall while being inverted so that the outer film is inside with the compressed air or water in the existing pipeline, and pressurized. When using a thermosetting resin composition, hot water is passed through, and in the photocurable resin composition, a plurality of light radiation sources are connected and moved in the pipeline while irradiating ultraviolet rays at a constant speed. The tube lining material is cured, and a structure is formed inside the tube. The irradiation time from the light radiation source varies depending on the effective wavelength region of the light source, the output, the irradiation distance, the thickness of the tubular lining material, etc., but is 0.05 to 1 hour, preferably 0.05 to 0.5 hour. It is. If it is less than 0.01 hours, the internal resin is in an uncured state, and more than 1 hour is not economical.

  As the photopolymerization initiator used in the curable resin composition of the present invention, a known ultraviolet polymerization initiator and / or a visible light polymerization initiator that can be cured even with a thick film can be used. Examples of UV polymerization initiators include benzoin ether-based isopropyl benzoin ether, isobutyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, benzyl ketal-based hydrocyclohexyl phenyl ketone, benzyl dimethyl ketal, ketone benzophenone-based benzyl, methyl- O-benzoinbenzoate, 2-chlorothioxanthone, methylthioxanthone, benzophenone-based benzophenone / tertiary amine, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone, acylophosphine oxide, bisacylphosphine oxide, camphorquinone, etc. It can be mentioned as a representative example. In the case of the photo-curing tubular lining material used in the present invention, a coating method is adopted in which ultraviolet rays are inserted into the inside of the tube and irradiated with ultraviolet rays for rapid curing. A photopolymerization initiator having absorption of 250 nm in the ultraviolet wavelength region to 450 nm in the visible wavelength region is preferable. 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzylmethyl ketal are preferred and may be used alone or in combination.

  An acylphosphine oxide compound is effective as a visible light polymerization initiator. Examples include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl). -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4 , 6-trimethylbenzoyl-diphenylphosphine oxide and the like. It may be used alone or in combination.

  The amount of the photopolymerization initiator used is the total amount of (A) to (E) which is a component constituting the resin composition used in the present invention {ie (A) to (C) ((D) and / or When (E) is used, the total content including them)} is in the range of 0.01 to 20% by mass. If it is less than 0.01% by mass, the polymerization may not be sufficiently performed, and if it is 20% by mass or more, the curing time is almost flat.

  Examples of the organic peroxide used when thermosetting the curable resin composition in the present invention include ketone peroxides such as methyl ethyl ketone peroxide; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide. Peroxyesters such as t-butylperoxyoctate and t-butylperoxybenzoate; Dialkyl peroxides such as dicumyl peroxide; Diacyl peroxides such as lauroyl peroxide and benzoyl peroxide Etc.

  The amount of the organic peroxide used is the total amount of (A) to (E) which is a component constituting the curable resin composition used in the present invention {ie (A) to (C) ((D) and In general, when (E) is used, it is generally in the range of 0.01 to 10% by mass relative to the total amount including them. When the amount is less than 0.1% by mass, the curing polymerization may not be sufficiently performed. When the amount exceeds 10% by mass, the curing time is not shortened.

  In the present invention, the total amount of (A) to (E) which is a component of the curable resin composition {that is, when (A) to (C) ((D) and / or (E) is used] 0.01-5 parts by mass of aromatic amine accelerator and / or polyvalent metal salt and / or complex with respect to the total amount including them)}, and then mixing an organic peroxide to form a thermosetting resin. It is preferable to warm the tubular lining material which formed the composition and impregnated the fibrous cylindrical body. The above accelerators and the like are effective for promoting curing. If the addition amount of the accelerator or the like 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.

  The resin composition used in the present invention can be used alone. However, in consideration of the sick house problem and the regulation of styrene emission concentration by the PRTR method, the following polymerization for crosslinking is considered. It can also be used as a resin composition in which a polymerizable monomer for crosslinking having a high vapor pressure is significantly reduced by using a polymerizable vinyl monomer in combination.

  Examples of polymerizable vinyl monomers for crosslinking include aromatic vinyl monomers such as styrene, vinyltoluene and α-methylstyrene; methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and 2-ethylhexyl methacrylate. Can be mentioned. These crosslinking polymerizable monomers may be used alone or in combination of two or more. Generally, styrene is used. The compounding amount of the crosslinkable polymerizable monomer is a resin composition of (A) to (E) {that is, (A) to (C) (when (D) and / or (E) is used, the whole including them)] It is preferably 30% by mass or less (the content of the polymerizable monomer for crosslinking is 23% or less) based on the product. The content of the crosslinkable polymerizable monomer in a normal vinyl ester resin (or a mixture thereof when an unsaturated polyester resin is used) is 40 to 50% by mass. For this reason, the content of the crosslinkable polymerizable monomer is greatly reduced, and the low volatility polymerizable monomer-containing resin composition capable of remarkably reducing the amount of volatilization during work is used without impairing the gist of the present invention. can do.

  Although it is the characteristic that it is excellent in drying property only with the component of the resin composition of this invention, you may use paraffin and / or wax together in order to improve drying property more.

  Examples of paraffins and / or waxes used in the curable resin composition of the present invention include paraffins such as paraffin wax and polyethylene wax; higher fatty acids such as stearic acid and 1,2-hydroxystearic acid. Although possible, paraffin wax is preferred. These paraffins and / or waxes are added for the purpose of improving the air blocking action and stain resistance during the curing reaction on the coating film surface. The addition rate is 0 with respect to the total amount of the components (A) to (E) {that is, (A) to (C) (the total including them when (D) and / or (E) is used)}. 0.1 to 5% by mass, preferably 0.2 to 2% by mass.

  Examples of the inert fine particle and / or granular inorganic aggregate material used in the present invention include sand, silica powder, crushed rock, calcium carbonate, alumina powder, clay, silica powder, talc, glass powder, silica powder, and water. Aluminum oxide, silica sand, aluminum silicate, magnesium silicate, cement and the like can be used.

  When an inert particulate and / or granular inorganic aggregate material is used, the amount used is a resin composition in the case of a tubular lining material in which a fibrous cylindrical body is impregnated with a thermosetting resin composition. 30% by mass or less is preferable based on the total amount of (A) to (E) {that is, (A) to (C) (the total including them when (D) and / or (E) is used)}. . This is because, when mixed in a large amount, the impregnation property is lowered, while the thermal conductivity is increased, and the curing time with warm air and hot water of a heating heat source is prolonged. Moreover, in the tubular lining material using the photocurable resin composition mixed with the inorganic aggregate material, it is difficult to transmit ultraviolet rays, so that only a small amount of a specific filler can be mixed. In this case, the blending amount is the total amount of the resin compositions (A) to (E) {that is, (A) to (C) (the total including them when (D) and / or (E) is used)} The amount is preferably 10% by mass or less.

  Furthermore, glass flakes, mica flakes, and the like can be used as the scaly inorganic filler in the curable resin composition of the present invention. The average particle size of the scaly inorganic filler is generally in the range of 10 to 4000 μm. In order to maintain the impregnation property of the resin composition into the fibrous cylindrical body and to maintain the anticorrosion durability, the average particle size is 100. ˜3000 μm, blending amount is total amount of resin compositions (A) to (E) {ie (A) to (C) (when (D) and / or (E) is used, the whole including them)} 10 mass% or less is preferable with respect to this. In addition, it is preferable to use a glass flake as the scale-like inorganic filler from the viewpoint of water absorption weight stability.

  In addition, these thermosetting resin compositions or photocurable resin compositions further include pigments, antioxidants, flow control agents, thixotropic agents, plasticizers, antishrink agents, antifoaming agents, colorants, and polymerization agents. Inhibitors and the like can be added as necessary.

  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.

[Example 1]
A resin composition containing A) unsaturated polyester and (B) dicyclopentenyloxyethyl acrylate was prepared as follows.

<Manufacture of unsaturated polyester>
In a 2 liter four-necked flask equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and thermometer, neopentyl glycol 4 mol (416 g), propylene glycol 1 mol (76 g), isophthalic acid 2 mol (332 g) Then, 3 mol (294 g) of maleic anhydride was dividedly added in a two-step reaction according to a conventional method, and reacted at 200 ° C. until the acid value reached 20 KOH mg / g. Thereafter, the obtained unsaturated polyester was cooled to 130 ° C., and 0.015 parts by mass was added to 100 parts by mass of the obtained unsaturated polyester, and dissolved at a temperature of 60 ° C. The unsaturated polyester obtained had a number average molecular weight of 2600, M _w / M _n of 3.2, and a hydroxyl value of 23 KOH mg / g.

  The number average molecular weight and the weight average molecular weight were measured using a GPC method (gel permeation chromatography method). The molecular weight value is a polystyrene equivalent value. A high-speed GPC device (HLC-8120GPC, manufactured by Tosoh Corp.) was used as a measuring device, and shodex KF-805, 803, 802 (manufactured by Showa Denko KK) were used as columns.

<Manufacture of resin composition>
To 56 parts by mass of the obtained unsaturated polyester, 20 parts by mass of dicyclopentenyloxyethyl acrylate (FA-512MT, manufactured by Hitachi Chemical Co., Ltd.) having a viscosity of 20 mPa · s and a molecular weight of 248 at 25 ° C. and a viscosity of 25 ° C. Was dissolved by adding 20 parts by mass of benzyl methacrylate (BzMA, manufactured by Mitsubishi Gas Chemical Co., Inc.) having a molecular weight of 176.5 at 3 mPa · s, then cooled to room temperature, and then average particle size of 1.9 μm, weight 4 parts by mass of polymethyl methacrylate resin powder (Zeon F320, manufactured by Zeon Kasei Co., Ltd.) having an average degree of polymerization of 30,000 was added and dissolved to obtain a resin mixture.

  Next, other compounds shown in Table 1 were added to and dissolved in the obtained resin mixture, and the resin composition for photo-curing laminated lining material (1-1) and the resin composition for thermosetting laminated lining material (1- 2) were prepared, and the characteristics obtained were evaluated. Details are shown below.

Light-curing laminated lining material:
The laminate specimen size used in the production of the following lining material photocured laminate is 1 m × 1 m.

To 100 parts by mass of the resin mixture, 1 part by mass of a photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO, manufactured by BASF) is thoroughly stirred and mixed to obtain a resin composition for a photocuring laminated lining material. A product (1-1) was obtained. First, a 0.2 mm thick polyurethane elastomer film, 790M60K (manufactured by Nippon Valqua Industry Co., Ltd.) is laid, and a roving cloth ERW580-554A (manufactured by Central Glass Co., Ltd.) with a unit weight of 600 g / m ² is overlaid thereon. And then impregnating the resin composition in the same manner as the intermediate layer with a chopped strand mat ECM600-501 (manufactured by Central Glass Co., Ltd.) having a unit weight of 600 g / m ^2. A polyurethane elastomer film of 790M60K (manufactured by Nippon Valqua Industries Co., Ltd.) having the same thickness as the first one was coated thereon to produce a photo-curing laminated lining material. The impregnation amount of the resin composition for a photo-curing laminated lining material was 4200 g / m ² . Thus, a laminated lining material (FRP lining material) was produced.

Thermosetting laminated lining material:
The laminated specimen size used in the production of the following lining material thermosetting laminate is 1 m × 1 m.

  As shown in Table 1, 1.5 parts by mass of organic peroxide / curing agent 328 (manufactured by Kayaku Akzo Co., Ltd.) is thoroughly stirred and mixed with 100 parts by mass of the resin mixture, and then the resin composition for the thermosetting laminated lining material. A thermosetting laminated lining material was produced in the same manner as the photocuring laminated lining material, except that the product (1-2) was used.

[Evaluation methods]
hardness:
The surface of the laminated lining material is irradiated with an ultraviolet lamp having a height of 15 cm to 400 W for 5 minutes, and then the hardness is measured with a Barcoll hardness meter (model: GYXJ934-1). Evaluation was good.

  The heat curing was evaluated by curing the laminated lining material by allowing it to stand at 25 ° C. for 24 hours and then curing and curing at 60 ° C. for 10 hours.

Surface drying time:
It produced using the applicator on a 20 degreeC room temperature glass plate, and obtained by implementing a finger touch test about surface dryness. The evaluation method of the finger touch test was to measure 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.

Average particle size (average single particle size):
(When the average particle size is 10 μm or less) Using a sample in which 0.2 g of thermoplastic resin is added to 100 ml of water and dispersed with ultrasonic waves, an observation photograph of 10,000 times of a transmission electron microscope is taken to obtain a single particle The length of 800 ± 100 pieces was measured, and the average value of the number-based lengths was obtained.

Thermoplastic resin weight average molecular weight:
It was measured by the solution specific viscosity method. The ratio of the viscosity of 35 ° C. of a solution obtained by dissolving 0.2 g of a sample resin in 50 ml of tetrahydrofuran to the solvent viscosity at the same temperature was determined, and the relationship between specific viscosity and weight average molecular weight determined in advance with various standard polystyrenes with known weight average molecular weights. From this, the average molecular weight of the sample resin is known.

Peelability:
For photo-curing lining materials;
After the surface temperature of the laminated lining material reaches room temperature after UV irradiation, JIS-Z-1524 and a cloth adhesive tape for packaging (width 50 mm, length 250 mm) are pressure-bonded to the surfaces of the upper and lower polyurethane elastomer films. Then, it was peeled from one end, the adhesive strength was measured, and the difficulty of peeling was determined.

For thermosetting lining materials;
The laminated lining material is allowed to stand at 25 ° C. for 24 hours, and then cured and cured at 60 ° C. for 10 hours, and then the JIS-Z-1524 / cloth adhesive tape for packaging (width 50 mm, length 250 mm) is applied to the surfaces of the upper and lower polyurethane elastomer films. ) Was peeled from one end, and the adhesive force was measured to determine the difficulty of peeling.

Tensile strength, tensile modulus:
As the properties of the cured laminate, the tensile strength and tensile modulus were measured according to JIS-K-7113.

Flexural strength, flexural modulus:
As physical properties of the cured laminate, bending strength and flexural modulus were measured according to JIS-K-7203.

Weight change rate:
10 g of a resin composition in which a photopolymerization initiator or a thermal polymerization initiator and an organic peroxide were mixed was poured into a glass petri dish having a diameter of 40 mm (height, 15 mm), and each was photopolymerized or thermally polymerized and cured, and then demolded. After the casting was immersed in warm water (80 ° C.) for 96 hours, the rate of weight change was measured.

Styrene volatilization:
After thoroughly stirring and mixing the resin composition, 100 g was put in a glass petri dish with a diameter of 145 mm, left to stand in an environment of a temperature of 25 ° C. and a humidity of 45% for 60 minutes, and then mixed, and the weight change rate was measured.

Viscosity for thickening properties:
A resin composition in which a photopolymerization initiator or an organic peroxide / curing agent 328 is mixed in a measuring container of a Brookfield viscometer (BF rotary viscometer) is collected, and a liquid temperature of 25 ° C. and environmental conditions are collected. (Measured at a room temperature of 23 ° C. and a humidity of 60%). Within 3 hours of measurement over time, the change in thickening was measured with the RVT model for medium viscosity measurement, and thereafter with the HBT model for high viscosity measurement.

  The results are shown in Table 1.

[Example 2]
(A) Unsaturated polyester, (B) Dicyclopentenyloxyethyl methacrylate and neopentyl glycol dimethacrylate, (C) Thickener for thermoplastic resin powder, and (D) Ethoxylated 4.0 moles of ethoxylation The composition of the resin composition using bisphenol A dimethacrylate is shown below.

<Manufacture of unsaturated polyester>
In a 2 liter four-necked flask equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and thermometer, 3 moles of propylene glycol (228 g), 2 moles of ethylene glycol (124 g), 3 moles of phthalic anhydride (444 g) Then, 2 mol (196 g) of maleic anhydride was added in a two-stage reaction according to a conventional method and reacted at 200 ° C. until the acid value reached 10 KOH mg / g. Thereafter, the obtained unsaturated polyester was cooled to 130 ° C., and 0.015 parts by mass was added to 100 parts by mass of the obtained unsaturated polyester, and dissolved at a temperature of 60 ° C. The unsaturated polyester obtained had a number average molecular weight of 3000, M _w / M _n of 3.2, and a hydroxyl value of 27 KOH mg / g.

<Manufacture of resin composition>
To 51 parts by mass of this unsaturated polyester, 17.5 parts by mass of dicyclopentenyloxyethyl methacrylate having the viscosity and molecular weight used in Example 1, a viscosity of 5 mPa · s at 25 ° C., and a neopentyl glycol dimethacrylate having a molecular weight of 240 17.5 parts by mass of acrylate (NK ester NPG, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 4.0 mol addition ethylene oxide bisphenol A dimethacrylate (BPE-200, Shin-Nakamura Chemical Co., Ltd.) 10 After adding part by mass and dissolving, cooled to room temperature, then added 4 parts by mass of methyl methacrylate copolymer powder (Zeon F320, manufactured by Zeon Kasei) having an average particle size of 1.8 μm and a weight average polymerization degree of 20,000. It melt | dissolved and the resin mixture was obtained.

  Next, other compounds shown in Table 1 were added to and dissolved in the obtained resin mixture, and the resin composition for photo-curing laminated lining material (2-1) and the resin composition for thermosetting laminated lining material (2- 2) were prepared, and the characteristics obtained were evaluated. Details are shown below.

Light-curing laminated lining material:
The laminate specimen size used in the production of the following lining material photocured laminate is 1 m × 1 m.

To 100 parts by mass of the resin mixture, 1 part by mass of a photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO, manufactured by BASF) is thoroughly stirred and mixed to obtain a resin composition for a photocuring laminated lining material. A product (2-1) was obtained. First, a 0.2 mm thick polyurethane elastomer film, 790M60K (manufactured by Nippon Valqua Industries Co., Ltd.) is laid, and a roving cloth ERW580-554A (manufactured by Central Glass Co., Ltd.) with a unit weight of 600 g / m ² is overlaid thereon. the resin composition was impregnated, it was then impregnated with the intermediate layer as a unit weight 600 g / m ² chopped strand mat ECM600-501 (manufactured by Central Glass Co.) was overlaid resin composition thereon Similarly, the last A polyurethane elastomer film of 790M60K (manufactured by Nippon Valqua Industries Co., Ltd.) having the same thickness as the first one was coated thereon to produce a photo-curing laminated lining material. The impregnation amount of the resin composition for a photo-curing laminated lining material was 4200 g / m ² . Thus, a laminated lining material (FRP lining material) was produced.

Thermosetting laminated lining material:
The laminated specimen size used in the production of the following lining material thermosetting laminate is 1 m × 1 m.

  As shown in Table 1, 1.5 parts by mass of organic peroxide / curing agent 328 (manufactured by Kayaku Akzo Co., Ltd.) is thoroughly stirred and mixed with 100 parts by mass of the resin mixture, and then the resin composition for the thermosetting laminated lining material. A thermosetting laminated lining material was produced in the same manner as the photocuring laminated lining material, except that the product (2-2) was used.

  The evaluation method was the same as in Example 1.

The results are shown in Table 1.
[Example 3]
(A) Unsaturated polyester, (B) Dicyclopentenyloxyethyl methacrylate, neopentyl glycol dimethacrylate and benzyl methacrylate, (C) Thickener for thermoplastic resin powder, and (E) Aromatic epoxy acrylate The composition of the resin composition was as follows.

<Manufacture of unsaturated polyester>
In a 2 liter four-necked flask equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and thermometer, neopentyl glycol 4 mol (416 g), propylene glycol 1 mol (76 g), isophthalic acid 2 mol (332 g) Then, 3 mol (294 g) of maleic anhydride was dividedly added in a two-step reaction according to a conventional method, and reacted at 200 ° C. until the acid value reached 20 KOH mg / g. Thereafter, the obtained unsaturated polyester was cooled to 130 ° C., and 0.015 parts by mass was added to 100 parts by mass of the obtained unsaturated polyester, and dissolved at a temperature of 60 ° C. The unsaturated polyester obtained had a number average molecular weight of 2500, M _w / M _n of 3.0, and a hydroxyl value of 25 KOH mg / g.

<Manufacture of resin composition>
To 48 parts by mass of this unsaturated polyester, 9 parts by mass of dicyclopentenyloxyethyl methacrylate having a viscosity of 17 mPa · s at 25 ° C. and a molecular weight of 262, benzyl meta having a viscosity of 3 mPa · s at 25 ° C. and a molecular weight of 176.5 20 parts by mass of acrylate (BzMA, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 9 parts by mass of neopentyl glycol dimethacrylate having a viscosity of 5 mPa · s at 25 ° C. and a molecular weight of 240, and an aromatic epoxy acrylate (epoxy ester 3000A, Kyoeisha Chemical Co., Ltd.) 10 parts by mass was added and dissolved, cooled to room temperature, then polymethyl methacrylate resin powder (Zeon F320, manufactured by Zeon Kasei Co., Ltd.) having an average particle size of 1.9 μm and a weight average polymerization degree of 30,000. ) 4 parts by mass was added and dissolved to obtain a resin mixture.

  Next, other compounds shown in Table 1 were added to and dissolved in the obtained resin mixture, and the resin composition for photo-curing laminated lining material (3-1) and the resin composition for thermosetting laminated lining material (3- 2) were prepared, and the characteristics obtained were evaluated. Details are shown below.

Light-curing laminated lining material:
The laminate specimen size used in the production of the following lining material photocured laminate is 1 m × 1 m.

A resin composition for a photo-curing laminated lining material is obtained by thoroughly stirring and mixing 1 part by mass of a photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF, Lucyrin TPO) with 100 parts by mass of the resin mixture. A product (3-1) was obtained. First, a 0.2 mm thick polyurethane elastomer film, 790M60K (manufactured by Nippon Valqua Industries Co., Ltd.) is laid, and a roving cloth ERW580-554A (manufactured by Central Glass Co., Ltd.) with a unit weight of 600 g / m ² is overlaid thereon. And then impregnating the resin composition in the same manner as the intermediate layer with a chopped strand mat ECM600-501 (manufactured by Central Glass Co., Ltd.) having a unit weight of 600 g / m ^2. A polyurethane elastomer film of 790M60K (manufactured by Nippon Valqua Industries Co., Ltd.) having the same thickness as the first one was coated thereon to produce a photo-curing laminated lining material. The impregnation amount of the resin composition for a photo-curing laminated lining material was 4200 g / m ² . Thus, a laminated lining material (FRP lining material) was produced.

Thermosetting laminated lining material:
The laminated specimen size used in the production of the following lining material thermosetting laminate is 1 m × 1 m.
As shown in Table 1, 1.5 parts by mass of organic peroxide / curing agent 328 (manufactured by Kayaku Akzo Co., Ltd.) is thoroughly stirred and mixed with 100 parts by mass of the resin mixture, and then the resin composition for the thermosetting laminated lining material. A thermosetting laminated lining material was produced in the same manner as the photocuring laminated lining material, except that the product (3-2) was used.

  The evaluation method was the same as in Example 1.

  The results are shown in Table 1.

[Example 4]
A) unsaturated polyester, (B) dicyclopentenyloxyethyl methacrylate and neopentyl glycol dimethacrylate, (C) thickener for thermoplastic resin powder, (D) ethylene oxide 10 mol addition ethoxylated bisphenol A dimethacrylate and ( E) A resin composition containing an aromatic epoxy acrylate was produced as follows.

<Manufacture of unsaturated polyester>
In a 2 liter four-necked flask equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and thermometer, neopentyl glycol 4 mol (416 g), propylene glycol 1 mol (76 g), isophthalic acid 2 mol (332 g) Then, 3 mol (294 g) of maleic anhydride was dividedly added in a two-step reaction according to a conventional method, and reacted at 200 ° C. until the acid value reached 20 KOH mg / g. Thereafter, the obtained unsaturated polyester was cooled to 130 ° C., and 0.015 parts by mass was added to 100 parts by mass of the obtained unsaturated polyester, and dissolved at a temperature of 60 ° C. The unsaturated polyester obtained had a number average molecular weight of 2700, M _w / M _n of 3.0, and a hydroxyl value of 25 KOH mg / g.

<Manufacture of resin composition>
To 40 parts by mass of the unsaturated polyester, 18 parts by mass of dicyclopentenyloxyethyl methacrylate having the above characteristic values, 18 parts by mass of neopentyl glycol dimethacrylate, 10 mol of ethylene oxide addition ethoxylated bisphenol A dimethacrylate (BPE-500 , Shin-Nakamura Chemical Co., Ltd.) and 10 parts by mass of aromatic epoxy acrylate (epoxy ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.), dissolved, cooled to room temperature, and then average particle size of 1.9 μm and weight 4 parts by mass of polymethyl methacrylate resin powder (Zeon F320, manufactured by Zeon Kasei Co., Ltd.) having an average polymerization degree of 30,000 was added and dissolved to obtain a resin mixture.

  Next, other compounds shown in Table 1 were added to and dissolved in the obtained resin mixture, and the resin composition for photo-curing laminated lining material (4-1) and the resin composition for thermosetting laminated lining material (4- 2) was prepared, and each characteristic was evaluated. Details are shown below.

Light-curing laminated lining material:
The laminate specimen size used in the production of the following lining material photocured laminate is 1 m × 1 m.

To 100 parts by mass of the resin mixture, 1 part by mass of a photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO, manufactured by BASF) is thoroughly stirred and mixed to obtain a resin composition for a photocuring laminated lining material. A product (4-1) was obtained. First, a 0.2 mm thick polyurethane elastomer film, 790M60K (manufactured by Nippon Valqua Industry Co., Ltd.) is laid, and a roving cloth ERW580-554A (manufactured by Central Glass Co., Ltd.) with a unit weight of 600 g / m ² is overlaid thereon. And then impregnating the resin composition in the same manner as the intermediate layer with a chopped strand mat ECM600-501 (manufactured by Central Glass Co., Ltd.) having a unit weight of 600 g / m ^2. A polyurethane elastomer film of 790M60K (manufactured by Nippon Valqua Industry Co., Ltd.) having the same thickness as the first one was coated thereon to produce a photo-curing laminated lining material. The impregnation amount of the resin composition for a photo-curing laminated lining material was 4200 g / m ² . Thus, a laminated lining material (FRP lining material) was produced.

Thermosetting laminated lining material:
The laminate specimen size used in the production of the following lining material thermosetting laminate is 1 m × 1 m.

  A thermosetting laminated lining material was produced in the same manner as the photocuring laminated lining material, except that the resin composition for thermosetting laminated lining material (4-2) shown in Table 1 was used.

  The evaluation method was the same as in Example 1.

  The results are shown in Table 1.

[Example 5]
<Manufacture of resin composition>
To 100 parts by mass of each of the resin mixtures obtained in Examples 1 to 4, 1 part by mass of a photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO, manufactured by BASF) was sufficiently added. The mixture was stirred and mixed to obtain a resin composition containing a photopolymerization initiator.

  Next, the obtained resin composition is shown in Table 2 as a resin composition for photo-curing laminated lining materials (5-1 to 8). The characteristics obtained from each were evaluated and are shown in Table 2. Details are shown below.

  An example on the outside of two steel mandrels having an outer diameter of 250 mm (inner diameter of 240 mm) (5-1, 3, 5, 7) and an outer diameter of 300 mm (inner diameter of 290 mm) (5-2, 4, 6, 8) After winding the same urethane elastomer film as described in 1 and heat-sealing the butt portion of the film portion to form a tubular tube, the resin is impregnated with the same laminated structure as in Example 1, and then the urethane elastomer film tube is A photo-curing tubular lining material was produced by covering the surface layer.

  This lining material is inverted and inserted into the pipe line of a fume tube whose inner surface is coated with a release agent, and is brought into close contact with the inner surface of the pipe line, and then a 400 W ultraviolet lamp is irradiated to the pipe line within the irradiation distance (the inner surface of the tubular lining material and the ultraviolet lamp). And 10 minutes at 5 cm to obtain a cured laminated tube.

  The cured laminated tube was removed from the pipeline and the items in Table 2 were evaluated. The obtained laminated tube (tube body) had an inner diameter of 248 mm in 5-1, 3, 5, and 7 and 298 mm in 5-2, 4, 6, and 8.

[Evaluation methods]
Peelability of inner and outer tube:
It confirmed by the method similar to Example 1. FIG.

Line load at the time of flattening and crushing as 5% as characteristics of hardened laminated tube:
It measured based on Japan Sewerage Association standard (JAWAS * K-1).

Watertightness and fracture water pressure confirmation test:
Measured according to JIS-K-6741: VU tube (hard vinyl chloride tube).

Thickening with time:
The viscosity increase with time of the resin composition mixed with the thickener was measured.

[Example 6]
<Manufacture of resin composition>
To 100 parts by mass of each of the resin compositions obtained in Examples 1 to 4, 1.5 parts by mass of an organic peroxide (curing agent 328, manufactured by Kayaku Akzo Co., Ltd.) is added and sufficiently stirred and mixed. Thus, a thickener and an organic oxide-containing resin composition were obtained.

  Next, the obtained resin composition is shown in Table 3 as a resin composition for thermosetting laminated lining materials (6-1 to 8). Each characteristic was evaluated and shown in Table 3. Details are shown below.

  Examples are provided on the outside of two steel mandrels having an outer diameter of 200 mm (inner diameter of 190 mm) (6-1, 3, 5, 7) and an outer diameter of 300 mm (inner diameter of 290 mm) (6-2, 4, 6, 8). After winding the same urethane elastomer film as described in No. 1 and heat-sealing the butt portion of the film portion to form a tubular tube, the resin is impregnated with the same laminated structure as in Example 1, and then the urethane elastomer film tube is coated on the surface layer. A thermosetting tube lining material was produced by coating with

  This lining material is inverted and inserted into a pipe line of a fume pipe whose inner surface is coated with a release agent, and is brought into close contact with the inner face of the pipe line. Then, warm water is introduced into the pipe line, and the initial temperature of the environment and the lining material is reduced from 20 ° C to 0 ° C. The temperature was raised at 5 ° C./min for 2 hours, and after 2 hours reached 80 ° C., maintained at 80 ° C. for 2 hours and then cooled to obtain a cured laminated tube.

  The cured laminated tube was demolded from the pipeline, and the same 5% flat load and crushing line load, water tightness, and fracture hydraulic pressure test as in Example 5 were performed. Table 3 shows the test results. The obtained laminated tube (tube body) had an inner diameter of 198 mm in 6-1, 3, 5, and 7 and 298 mm in 6-2, 4, 6, and 8.

[Example 7]
In Example 1-1, a photo-curing laminated lining material was prepared using 0.188 μm-thick polyester film Lumirror S10 # 188 (manufactured by Toray Industries, Inc.) instead of the inner / outer surface film / polyurethane elastomer. . The irradiation position, irradiation capacity, and irradiation time of the ultraviolet lamp were the same as in Example 1. In the same manner as in Example 1, the hardness, film peelability, and cured laminate physical properties of the cured laminated lining material were evaluated. The results are shown in Table 4.

[Example 8 and Comparative Examples 1 and 2]
The blending of the resin composition using (A) unsaturated polyester, (B) dicyclopentenyloxyethyl methacrylate and benzyl methacrylate, and (C) a thickening agent for thermoplastic resin powder is shown below.

<Manufacture of unsaturated polyester>
In a reaction vessel of a 2 liter four-necked flask equipped with a stirrer, reflux condenser, nitrogen gas inlet tube, and thermometer, neopentyl glycol 4 mol (416 g), propylene glycol 1 mol (76 g), isophthalic acid 2 mol (332 g) and 3 mol (294 g) of maleic anhydride were dividedly charged in a two-step reaction according to a conventional method, and reacted at 200 ° C. until the acid value reached 17 KOH mg / g. Thereafter, the obtained unsaturated polyester was cooled to 130 ° C., 0.015 part by mass was added to 100 parts by mass of the obtained unsaturated polyester, and dissolved at a temperature of 60 ° C. The unsaturated polyester obtained had a number average molecular weight of 2,800, _Mw / _Mn of 3.2, and a hydroxyl value of 23 KOHmg / g.
<Manufacture of resin composition>
To 58 parts by mass of the obtained unsaturated polyester, 19 parts by mass of dicyclopentenyloxyethyl methacrylate (FA-512MT, manufactured by Hitachi Chemical Co., Ltd.) having a viscosity of 20 mPa · s and a molecular weight of 262 at 25 ° C. and 25 ° C. After adding 19 parts by mass of benzyl methacrylate (BzMA, manufactured by Mitsubishi Gas Chemical Co., Inc.) having a viscosity of 3 mPa · s and a molecular weight of 176.5, the mixture was cooled to room temperature, and then used as a thickening agent. Thermoplastic resin powder [polymethylmethacrylate resin powder (Zeon F320, manufactured by Zeon Kasei Co., Ltd.)] having a thickness of 9 μm and a weight average polymerization degree of 30,000, alkaline earth metal oxide / magnesium oxide (Kyowa Chemical) Kogyo Co., Ltd., Magmicron MD-4AM) and diphenylmethane diisocyanate (Mitsumi Takeda Chemica) as a compound having an isocyanate group Ltd., Kosumone - the door PH) was dissolved was added to the formulation shown in Table 5, to obtain a resin mixture.

  Next, other compounds shown in Table 5 were added to and dissolved in the obtained resin mixture to prepare a resin composition (8-1 to 5) for a photo-curing laminated lining material, and the viscosity change with time was evaluated. . The results are shown in Table 5.

  Example 8 is 8-1 to 3, Comparative Example 1 is 8-4, and Comparative Example 2 is 8-5.

[Comparative Example 3]
After adding 2 parts by weight of the organic peroxide of Example 6 (curing agent 328, manufactured by Kayaku Akzo Co., Ltd.) to 100 parts by weight of the styrene-type vinyl ester resin, the same method as in Example 6 was performed after thoroughly stirring and mixing. A cured laminate tube was obtained.

  The cured laminated tube was demolded from the conduit, and the peelability of the inner and outer surface chives was confirmed by the same method as in Example 1. In addition, as the cured laminated pipe properties, the line load and water tightness at the time of flattening at 5% and crushing, and the fracture water pressure confirmation test are the Japan Sewerage Association Standard (JSWAS · K-1) described in Example 5 and the rigid polyvinyl chloride pipe: Each measurement was made according to a VU tube (JISK6741).

The styrene volatilization amount was measured in the same manner as in Example 1. As shown in Table 6, the styrene volatilization amount was as high as 80 g / m ^2, and the polyurethane elastomer film was floated or softened due to swelling.

[Comparative Example 4]
In Comparative Example 1, a photocured laminate was prepared using a 0.2 mm thick polyethylene film instead of the inner and outer surface film polyurethane elastomer described in Example 1. As shown in Table 7, the polyethylene film was partially fused to the surface of the curable composite material, and peeling of the film was difficult.

  As is clear from the results shown in Tables 1 to 7, the curable resin composition of the present invention exhibited characteristics from the unsaturated polyester resin type when the FRP lining material and the tubular lining material were used. That is, compared with the conventional styrene type unsaturated polyester resin and vinyl ester resin types, not only odor but also thickening behavior (initial thickening stability, rapid thickening after impregnation of fibrous material) Imparted and viscosity stability over time) and film peelability were good, and also in laminated tube properties, those using the curable resin composition of the present invention showed superior properties than the conventional ones.

It is sectional drawing which shows an example of a structure of the tubular lining material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Tubular lining material 2 Inner membrane | film | coat 3 Fiber layer cylindrical body 4 Outer membrane | film | coat

Claims (14)

  (A) 30-70% by weight of an unsaturated polyester having a number average molecular weight of 500-4000 and an acid value of 5-30 KOHmg / g, and (B) 30-70% by weight of a monofunctional (meth) acrylate monomer, and (C) A curable resin composition comprising 1 to 30% by mass of a thickener made of thermoplastic resin powder, wherein the total of each mass% is 100% by mass.   (A) 30-70% by mass of an unsaturated polyester having a number average molecular weight of 500-4000 and an acid value of 5-30 KOHmg / g, (B) 30-70% by mass of a monofunctional (meth) acrylate monomer, and ( D) 5 to 20% by mass of an alkoxylated bisphenol A dimethacrylate having an alkylene oxide addition mole number of 2 to 20, and (C) 1 to 30% by mass of a thickener made of a thermoplastic resin powder. Is 100 mass%. Curable resin composition characterized by the above-mentioned.   A) 30 to 70% by mass of an unsaturated polyester having a number average molecular weight of 500 to 4000 and an acid value of 5 to 30 KOHmg / g, (B) 30 to 70% by mass of a monofunctional (meth) acrylate monomer, and (E ) 10 to 70% by mass of epoxy (meth) acrylate obtained by reaction of an aromatic epoxy resin and (meth) acrylic acid, and (C) 1 to 30% by mass of a thickener made of thermoplastic resin powder, The total of each mass% is 100 mass%, The curable resin composition characterized by the above-mentioned.   (A) 30 to 70% by mass of an unsaturated polyester having a number average molecular weight of 500 to 4000 and an acid value of 5 to 30 KOHmg / g, (B) 30 to 70% by mass of a monofunctional (meth) acrylate monomer, (D 10) Epoxy (meth) acrylate 10 obtained by reaction of 5-20% by mass of alkoxylated bisphenol A dimethacrylate having an alkylene oxide addition mole number of 2-20 and (E) aromatic epoxy resin and (meth) acrylic acid. A curable resin composition comprising -70% by mass and (C) 1-30% by mass of a thickener made of thermoplastic resin powder, and the total of each mass% is 100% by mass.   (B) The monofunctional (meth) acrylate monomer has a group containing a cyclic hydrocarbon group having at least one carbon-carbon double bond and / or at least one nitrogen atom in the ring as an alcohol residue. Curable resin composition of any one of Claims 1-4 containing a monofunctional (meth) acrylate type monomer.   (B) a monofunctional (meth) acrylate monomer having a group containing a cyclic hydrocarbon group having one carbon-carbon double bond in the ring as an alcohol residue, The curable resin composition according to any one of claims 1 to 4, further comprising a monofunctional (meth) acrylate monomer having a group containing a hydrocarbon group having an aromatic group as an alcohol residue. (From the examples)   Further, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,6 -Curability according to any one of claims 1 to 6, comprising at least one (F) polyfunctional (meth) acrylic monomer selected from hexanediol diacrylate and neopentyl glycol diacrylate. Resin composition. The curable resin composition according to any one of claims 1 to 7, wherein (A) the unsaturated polyester has a M _W / M _n of 4.0 or less.   (C) The average particle diameter of thermoplastic resin powder is 0.1-5.0 micrometers, The curable resin composition of any one of Claims 1-8.   A lining material comprising the curable resin composition according to any one of claims 1 to 9.   An inner surface of a tubular curable composite material obtained by impregnating a fiber layer cylindrical body with a photocurable resin composition containing the curable resin composition according to any one of claims 1 to 9 and a photopolymerization initiator, and Tubular lining material formed by covering the outer surface with at least one tube.   An inner surface of a tubular curable composite material obtained by impregnating a fiber layer cylindrical body with a thermosetting resin composition containing the curable resin composition according to any one of claims 1 to 9 and a thermal polymerization initiator, and Tubular lining material formed by covering the outer surface with at least one tube.   The oxide and / or hydroxide and / or metal alkoxide of alkaline-earth metal with respect to 100 mass parts of curable resin composition and curable resin composition of any one of Claims 1-9. The tubular lining material according to claim 11 or 12, which contains 0.3 to 10 parts by mass. The claim which contains 0.3-10 mass parts of 1 or more types of compounds which have an isocyanate group with respect to 100 mass parts of curable resin composition and curable resin composition of any one of Claims 1-9. Item 13. The tubular lining material according to Item 11 or 12.

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