JP3096806B2 - Lining material for pipe inner surface coating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel lining material for coating the inner surface of a pipe, which has a small shrinkage ratio when forming a coating film.

[0002]

2. Description of the Related Art An inner surface of a cast iron pipe for water supply or a concrete fume pipe for sewage is, for example, unsaturated polyester resin,
A lining material mainly composed of an unsaturated polymerizable monomer and a peroxide-based initiator is applied by mixing sand. However, since this lining material has a large shrinkage ratio when the coating film is cured, it has a defect that the coating film is liable to crack, peel, and the like.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lining material for coating the inner surface of a pipe, which has a small shrinkage upon curing of a coating film and does not cause cracking or peeling of the coating film.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that, in particular, the unsaturated polyester resin, the unsaturated polymerizable monomer and the peroxide-based initiator, It has been found that a composition comprising a (meth) acryloyl group-containing styrene macromonomer and the following flat particles has a small shrinkage ratio upon curing of a coating film, and does not cause cracking or peeling of the coating film, thereby completing the present invention. I came to.

That is, the present invention relates to (A) an unsaturated polyester resin, (B) an unsaturated polymerizable monomer, (C) a peroxide initiator, and (D) a styrene macromonomer containing a (meth) acryloyl group. And (E) a longitudinal diameter of about 80 μm or less
And inorganic flat particles, metal flat particles and
One or more selected from plastic-based flat particles
The present invention relates to a lining material for coating the inner surface of a pipe, wherein the lining material is mainly composed of the above flat particles.

When the lining material of the present invention is used for coating the inner surface of a pipe, its shrinkage upon curing of the coating film is small, so that cracks and peeling do not occur. Since it can be finished to a painted surface, the resistance to water during water supply can be further reduced. In addition, the chemical resistance and corrosion resistance of the coating film are good.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The pipe to which the lining material of the present invention can be applied is not particularly limited, but a cast iron pipe for water supply (inner diameter of about 200 to 3,000 mm) and a concrete fume pipe for sewage (inner diameter) which require the above performance are required. About 200 ~ 3,000
0 mm) and the like are particularly preferred.

Hereinafter, the lining material of the present invention will be specifically described.

Component (A): unsaturated polyester resin The resin is a polyester resin having two or more polymerizable double bonds in one molecule, and is mainly composed of an unsaturated polybasic acid and a polyhydric alcohol. It can be produced by a chemical reaction.

Unsaturated polybasic acids are compounds having one or more polymerizable unsaturated double bonds and two or more carboxyl groups in one molecule, for example, maleic acid, fumaric acid, mesaconic acid, Examples thereof include citraconic acid, itaconic acid and anhydrides thereof.

The polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, butanediol, hexanediol, hydrogenated Bisphenol A and the like.

Further, in the production of the unsaturated polyester resin, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, adipic acid, sebacic acid, Polybasic acids having no polymerizable double bond, such as het acids and anhydrides thereof, can also be used in combination. In the production of the unsaturated polyester resin, a monoalcohol or monobasic acid having one hydroxyl group or carboxyl group in one molecule can be used in combination, if necessary.

The unsaturated polyester resin (A) has a number average molecular weight of about 1,000 to about 50,000, especially about 2,000.
000 to about 10,000, hydroxyl value is 5 to 100 mgKOH /
g, especially 10-50 mgKOH / g, acid value 5-30 mgKOH / g,
In particular, it is preferably 9 to 18 mgKOH / g. Further, the unsaturated equivalent of the resin, that is, the number average molecular weight per double bond, is about 100 to about 1,000, especially about 150 to about 5
Preferably it is 00.

Component (B): unsaturated polymerizable monomer The monomer is a compound having one or more polymerizable double bonds in one molecule, and has a molecular weight higher than that of the component (A). Small, less than about 1,000 is preferred. The monomer is
It copolymerizes with the polymerizable double bond in the component (A) to crosslink and cure, and also acts as a solvent.

The monomer includes, for example, acrylic acid or methacrylic acid and a monoalcohol (aliphatic alcohol,
Monoesters with alicyclic alcohols, aromatic alcohols, ether group-containing alcohols, etc .; acrylic acid or methacrylic acid and dihydric or higher alcohols having 1 to 20 carbon atoms (aliphatic alcohols, alicyclic alcohols, aromatics) Hydroxyl-containing unsaturated monomers which are mono- or di-esterified products with alcohols, alcohols containing ether groups, etc .; unsaturated monomers containing carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid; glycidyl Glycidyl group-containing unsaturated monomers such as acrylate and glycidyl methacrylate; vinyl triethoxy silane, vinyl trimethoxy silane, vinyl tris (methoxy ethoxy) silane, γ-methacryloyloxy propyl trimethoxy silane, 2-styryl ethyl trimethoxy silane and the like Hydrolysable Al Kishishiran group-containing unsaturated monomer;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butane Diol diacrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate Compounds having two or more polymerizable double bonds in one molecule such as acrylate and pentaerythritol tetra (meth) acrylate; ethyl vinyl ether, n-propyl vinyl ether , Isopropyl vinyl ether,
Chain alkyl vinyl ethers such as butyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, and octyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and trivinylphenyl ether; Aralkyl vinyl ethers such as vinyl ether and phenethyl vinyl ether; vinyl acetate, vinyl propionate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate,
Vinyl esters such as vinyl isocaproate, vinyl pivalate, vinyl caprate, and verova monomer (trade name, manufactured by Shell Chemical Co., Ltd.); olefins such as ethylene, propylene, and butylene; fragrances such as styrene, α-methylstyrene, and vinyltoluene Group unsaturated monomers; other unsaturated monomers such as acrylonitrile and vinyl chloride; and the like. One or more of these can be used.

Component (C): peroxide initiator This is for accelerating the curing speed of the lining material of the present invention. Specifically, benzoyl peroxide, methyl ethyl ketone peroxide, di-t-butyl hydroperoxide, t-butyl hydroperoxide, cumyl peroxide, cumene hydroperoxide,
Diisopropylbenzene hydroperoxide, t-
Butylperoxybenzoate, lauryl peroxide, acetyl peroxide, t-butylperoxy-
Organic peroxides such as 2-ethylhexanoate are exemplified. One or more of these can be used.

Component (D): Styrene macromonomer containing (meth) acryloyl group This is a styrene macromonomer having one (meth) acryloyl group at one end. Specifically, a styrene monomer is polymerized in the presence of a radical polymerization initiator and a carboxyl group-containing mercaptan-based chain transfer agent to prepare a styrene macromonomer having a carboxyl group at one end, and then glycidyl acrylate is added to the carboxyl group. Alternatively, the component (D) can be obtained by subjecting glycidyl methacrylate to an esterification reaction and introducing a (meth) acryloyl group.

As the carboxyl group-containing mercaptan chain transfer agent, a compound represented by the general formula HS (R) COOH (where R is an alkylene group having 1 to 20 carbon atoms) is suitable. Examples of the alkylene group having 1 to 20 carbon atoms include methylene, ethylene, propylene,
Butylene and hexylene groups. Specific examples of the chain transfer agent include mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptocaproic acid, mercaptoundecylic acid, and mercaptopalmitic acid.

The number average molecular weight of the component (D) is as described in the above (B).
Suitably larger than the components, in the range of about 1,000 to about 10,000, especially about 2,000 to about 8,000.

Component (E): having a diameter in the longitudinal direction of about 80 μm or less and comprising inorganic flat particles, metal flat particles and
Or two selected from plastic and flat particles
Here more of the flat particles, longitudinal diameter of the flat particles is preferably about 3 to about 40 [mu] m, about 3 to about 1
More preferably, it is 5 μm. The thickness of the flat particles is preferably 1/2 or less of the longitudinal diameter. In terms of the material, there are inorganic, metal, and plastic materials having these shapes. Specifically, inorganic flat particles such as silica, talc, clay, barium sulfate, magnesium carbonate, gypsum, titanium oxide, iron oxide, and mica: metal flat particles such as aluminum: polyamide, etc. Plastic-based flat particles: are suitable. One or more of these can be used.

The lining material for coating the inner surface of a pipe according to the present invention contains the above components (A) to (E) as main components, and the composition ratio of these components can be arbitrarily selected according to the purpose. It is preferable to use them in a mixture at an appropriate ratio. That is, based on the solid content ratio, (B) the unsaturated polymerizable monomer is 5 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the unsaturated polyester resin.
(C) Peroxide initiator is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, and (D) (meth) acryloyl group-containing styrene macromonomer is 1 to 40 parts by weight, preferably 5 to 5 parts by weight. ２０20 parts by weight, (E) 5 to 500 flat particles
Parts by weight, preferably 10 to 300 parts by weight, are suitable.
These are mixed and dispersed together with an organic solvent for a paint, if necessary, to obtain the lining material of the present invention.

Examples of the organic solvent include hydrocarbon solvents such as hexane, heptane, toluene and xylene; alcohol solvents such as methanol, ethanol, butanol and octanol; and ether solvents such as diethyl ether, butyl cellosolve and diethylene glycol monobutyl ether. Examples thereof include solvents, ketone solvents such as methyl ethyl ketone and isophorone, and ester solvents such as ethyl acetate, butyl acetate, and cellosolve acetate, and at least one of them can be used.

The lining material of the present invention may further contain a curing catalyst such as cobalt naphthenate or lead naphthenate in an amount of 0.5 to 10 per 100 parts by weight of the unsaturated polyester resin (A).
It can be blended in a ratio of parts by weight. Further, sand or the like can be blended with the lining material.

The lining material of the present invention is obtained by mixing the above components, and the mixing order is not particularly limited. However, when a curing catalyst is used, both components are easily reacted with peroxide. It is preferable to use a two-pack type that is separated in advance and mixed immediately before use. In a system that does not use a curing catalyst, all components can be mixed to perform a one-pack type.

The method of coating (lining) the inner surface of the pipe with the lining material of the present invention is not particularly limited, but for example, airless spray, air spray, trowel or the like is used so that the cured coating film has a thickness of 0.5 to 6 mm. It is preferable to paint on. The coating is cross-linked and cured by leaving it at room temperature for 15 to 48 hours.

[0026]

EXAMPLES Examples and comparative examples of the present invention are shown below. Parts and percentages are in principle based on weight.

Examples 1 to 5 and Comparative Examples 1 to 3 Based on the components and amounts shown in Table 1, the components were blended and uniformly mixed to obtain a lining material. Agent I and Agent II were separately prepared, and the two components were mixed immediately before use.

[0028]

[Table 1]

The amounts in Table 1 above indicate parts by weight.
* 1 to * 6 in the table indicate the following.

* 1: "Polylite TP335B", manufactured by Dainippon Ink and Chemicals, Inc., trade name, number average molecular weight of about 2,7
This is a solution comprising 57% of an unsaturated polyester resin having a hydroxyl value of 30 mg KOH / g, an acid value of 14 mg KOH / g and an unsaturated equivalent of 200, and 43% of styrene. Here, the unsaturated polyester resin corresponds to the component (A), and styrene corresponds to the component (B).

* 2: A methacryloyl group-containing styrene macromonomer having a methacryloyl group introduced at one end of a styrene homopolymer, and having a number average molecular weight of 5,000.

* 3: Flat silica particles, longitudinal diameter 3
５5 μm, thickness 0.5-1 μm.

* 4: Flat talc particles, diameter 5 in the longitudinal direction
-10 μm, thickness 1-2 μm.

* 5: 50% aliphatic organic solvent solution of cobalt naphthenate (containing 6% as cobalt).

* 6: “Permec N”, manufactured by NOF Corporation
Trade name, methyl ethyl ketone peroxide.

Next, for each of the above lining materials, the volume shrinkage, the cold test, the viscosity and the smoothness were examined, and the performance was compared. The test method is as follows.

Volume shrinkage (%): Mixing the agents I and II of the lining material of the above composition,
Pour into a 20 mm high hollow cylindrical glass, cure at room temperature, measure the diameter before and after curing, based on {(volume before curing-volume after curing) / volume before curing} x 100 evaluated.

Cold test: A mixture of the above-mentioned agent I and agent II was applied to the inner surface of a rotating cast iron pipe having a diameter of 200 mm with a spray gun, and sand (No. 5 silica sand) was applied while the coated surface was wet. , Particle size range 20-100 mesh (840-
149 μm), 35-48 mesh (420-297 μm)
m) occupying the center) and mixed into the painted surface.
The weight ratio of the mixture to sand is 1 / 1.5, and the film thickness after mixing the sand is about 3 mm. After coating, leave the coating at room temperature for 24 hours to cure the coating, leave it at 5 ° C for 12 hours, then leave it at 60 ° C for 12 hours as one cycle, and repeat this until cracks, cracks, etc. occur on the coating. Was examined for the number of cycles.

Viscosity: Measured using a B-type viscometer (25 ° C.) in a system excluding the component (C) and the curing catalyst from the above composition.

Smoothness: The coated surface of the inner surface of the cast iron pipe coated in the same manner as in the cold test was visually evaluated. ○ indicates that the unevenness of the inner surface of the tube is eliminated and the smoothness is excellent, △ indicates that the unevenness of the inner surface of the tube is slightly recognized, and X indicates that the unevenness of the inner surface of the tube is clearly recognized, respectively.

Table 2 shows the test results.

[0042]

[Table 2]

[0043]

【The invention's effect】

(1) Since the shrinkage of the coating film at the time of curing was smaller than that of the conventional one, cracks and cracks were not generated on the coating film applied on the inner surface of the pipe.

(2) Even if there are irregularities on the inner surface of the pipe, the coating of the lining material eliminates the irregularities, makes the pipe smooth, and improves the water supply efficiency.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideki Otsu 1-12-19 Kitahorie, Nishi-ku, Osaka-shi, Osaka Inside Kurimoto Iron Works Co., Ltd. (72) Inventor Ken Yamamoto 1-1-12 Kitahorie, Nishi-ku, Osaka-shi, Osaka No. 19 Inside Kurimoto Iron Works Co., Ltd. (72) Nobuo Aoki Inventor 1-12-19 Kitahorie, Nishi-ku, Osaka City, Osaka Prefecture 72 Inside Kurimoto Iron Works Co., Ltd. No. 1 Kansai Paint Co., Ltd. (72) Inventor Osamu Tsurumoto 33-1, Kanzakicho, Amagasaki City, Hyogo Prefecture Inside Kansai Paint Co., Ltd. (72) Toshio Namba 33-1 Kanzakicho, Amagasaki City, Hyogo Kansai Inside Paint Co., Ltd. (72) Inventor Hirofumi Yamato 33-1, Kanzaki-cho, Amagasaki City, Hyogo Prefecture Inside Kansai Paint Co., Ltd. (56) References JP-A-3-1799062 (JP, A) JP-A-3 26711 (JP, A) JP-A-2-252186 (JP, A) JP-A-59-177177 (JP, A) JP-A-59-123574 (JP, A) JP-A-56-88416 (JP, A) JP-A-51-95434 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 4/00 C09D 167/06 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. An unsaturated polyester resin (A), an unsaturated polymerizable monomer (B), a peroxide initiator (C), and (D)
A (meth) acryloyl group-containing styrene macromonomer and (E) a longitudinal diameter of about 80 μm or less ,
Flat particles, metal flat particles and plastics
A lining material for coating the inner surface of a pipe, characterized by comprising one or more kinds of flat particles selected from flat particles as a main component. 2. The unsaturated polyester resin (A) has a number average molecular weight of about 1,000 to about 50,000 and a hydroxyl value of 5-1.
00 mg KOH / g, acid value 5-30 mg KOH / g, unsaturated equivalent 100
The lining material according to claim 1, wherein the lining material has a thickness of from 1,000 to 1,000. 3. The (meth) acryloyl group-containing styrene macromonomer (D) is a styrene macromonomer having one (meth) acryloyl group at one end.
Lining material described in. 4. A (meth) acryloyl group-containing styrene macromonomer (D) obtained by subjecting a styrene macromonomer having a carboxyl group at one end to an esterification reaction of glycidyl (meth) acrylate to introduce a (meth) acryloyl group. The lining material according to claim 1, which is: 5. A (meth) acryloyl group-containing styrene macromonomer (D) having a number average molecular weight of about 1,000 to about 1
The lining material according to claim 1, wherein the lining material is of 000. 6. A flat particle (E) having a longitudinal diameter of about 3
The lining material according to claim 1, wherein the thickness is from about 40 m to about 40 m. 7. An unsaturated polyester resin (A), 100 parts by weight, unsaturated polymerizable monomer (B) 5 to 200 parts by weight, peroxide initiator (C) 1 to 20 parts by weight, (Meta)
Acryloyl group-containing styrene macromonomer (D) 1
The lining material according to claim 1, wherein 40 parts by weight and 10 to 500 parts by weight of the flat particles (E) are blended.