JPH05170847A - Resin composition for flake lining - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which is excellent in lining properties and crack resistance during molding and curing and gives a lined molded article having an improved resistance to acid and alkali. CONSTITUTION:The title compsn. is prepd. by compounding 100 pts.wt. resin component consisting of 20-80wt.% unsaid. polyester or epoxy acrylate and 80-20wt.% polyethylene glycol di(meth)acrylate with 5-100 pts.wt. inorg. flake or by compounding 100 pts.wt. resin component consisting of 50-97wt.% mixture of 20-80wt.% unsatd. polyester with 80-20wt.% styrene and 97-50wt.% polyethylene glycol di(meth)acrylate with 5-100 pts.wt. inorg. flake.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a flare lining, which is excellent in high stretchability during lining, and whose lining molded product has particularly good corrosion resistance and crack resistance. This resin composition is a device used in a corrosive atmosphere such as various acids and alkalis, a marine structure suffering from salt damage,
It is used in various applications such as the bottom of oil tanks.

[0002]

2. Description of the Related Art Conventionally, in the above-mentioned field, a resin which causes curing by copolymerization between unsaturated bonds represented by unsaturated polyester resin and epoxy acrylate resin contains inorganic flakes. The following resin composition is used. At that time, an aromatic compound is introduced into the unsaturated polyester and epoxy acrylate resin skeleton in order to improve the toughness, hot water resistance, corrosion resistance and the like of the intended lining molded product. But,
In this method, if the adhesion between the lining molded product and the base material is lowered, or if the base material has a complicated shape, cracks occur in the lining molded product during molding and curing.

On the other hand, in order to solve this, in the resin composition, a method for reducing the content of unsaturated bonds in the main chain skeleton, a method for reducing the content of aromatic compounds, and Methods such as introducing a saturated aliphatic compound of a chain or introducing a compound exhibiting entropy elasticity such as a butadiene compound have been adopted. However, in any of these methods, in addition to the reduction in toughness and hot water resistance of the lining molded product, its corrosion resistance is particularly insufficient. An object of the present invention is to provide a resin composition which is excellent in crack resistance at the time of molding and curing and which can provide a lining molded product having good corrosion resistance.

[0004]

[Means for Solving the Problems] As a result of intensive studies for solving these problems, the present inventors have found that curing is caused by copolymerization between unsaturated bonds, and the resin containing inorganic flakes is cured. It was found that it is effective to include a specific copolymer composition, and the present invention has been completed.

That is, according to the present invention, 100 parts by weight of a prepolymer having at least two unsaturated bonds in the molecule has an ether bond and at least 2 ends of the molecule.
Copolymerizable monomer containing 4 acryloyl groups 25-4
The resin composition for flaking is characterized by containing 5 to 100 parts by weight of inorganic flakes with respect to 100 parts by weight of a resin containing 00 parts by weight. Further, the present invention is
A prepolymer having at least two unsaturated bonds in the molecule and 100 parts by weight of a resin composed of a monomer copolymerizable with the prepolymer have an ether bond and at least two at the end of the molecule. A resin containing 3 to 200 parts by weight of an acryloyl group-containing copolymerizable monomer
A resin composition for flaking, which comprises 5 to 100 parts by weight of inorganic flakes with respect to parts by weight.

First, the prepolymer used in the present invention having at least two unsaturated bonds in the molecule is a prepolymer having an unsaturated bond in the molecule and / or an unsaturated bond at the end of the molecular chain. It can be classified into three types.

Examples of those having an unsaturated bond in the molecule include unsaturated polyester. This unsaturated polyester is a commonly used unsaturated polyester, and comprises an α, β-unsaturated dibasic acid and a saturated dibasic acid,
And those obtained by esterification reaction with glycols. Examples of the above α, β-unsaturated dibasic acid include maleic anhydride, maleic acid, fumaric acid,
Itaconic acid and the like or alkyl esters thereof are suitable. As the saturated dibasic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, halogenated phthalic anhydride, adipic acid,
Succinic acid, sebacic acid and the like, or alkyl esters thereof are suitable. Further, as the glycols, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, hydrogenated bisphenol A, 2,2'-di (4-hydroxypropoxyphenyl) Suitable are propane, 2,2'-di (4-hydroxyethoxyphenyl) propane, ethylene oxide and the like. Regarding the above-mentioned unsaturated dibasic acid, saturated dibasic acid and glycols, a mixture of two or more kinds may be used, respectively, except that one kind of unsaturated dibasic acid and glycols must be contained.

Examples of the one having an unsaturated bond in the molecule and at the end of the molecular chain include those obtained by modifying the end of an unsaturated polyester with an acryloyl group. Examples of the modification method include esterification, epoxy ring-opening reaction, and modification by chemical reaction such as urethane addition.

Examples of compounds having at least two unsaturated bonds at the ends of the molecular chain include urethane acrylate and epoxy acrylate. This epoxy acrylate is obtained by a usual addition reaction of an epoxy compound having at least two epoxy groups at the molecular end with acrylic acid and / or methacrylic acid. Examples of the above-mentioned epoxy compounds include bisphenol A-based epoxy compounds and hydrogenated bisphenol A.
Epoxy compound (dimer) acid diglycidyl ester, polyalkylene ether epoxy compound, novolac epoxy compound, cycloaliphatic epoxy compound,
Brominated epoxy compound, polyglycidyl ether epoxy compound, diglycidyl ester epoxy compound,
Diglycidyl amino epoxy compounds, methyl epichloro epoxy compounds, spiro glycol epoxy compounds, diglycidyl ether epoxy compounds, orthocresol novolac epoxy compounds, cyclohexane epoxy compounds, bisphenol S epoxy compounds, polybutadiene epoxy compounds, etc. Is mentioned.

The monomer copolymerizable with the prepolymer having at least two unsaturated bonds in the molecule is usually a copolymerizable monomer of a resin which causes curing by copolymerization between unsaturated bonds. Is what is used. For example, alkenyl aromatic monomers such as styrene, α-methylstyrene, t-butylstyrene, vinyltoluene, acrylic acid, methacrylic acid, and their alkyl ethers are used, and styrene is particularly preferable. .. The compounding ratio of the prepolymer having at least two unsaturated bonds in the molecule and the monomer copolymerizable with the prepolymer is usually 20 to 80% by weight of the prepolymer and copolymerizable therewith. 80 to 20% by weight of monomer is suitable.

Next, the copolymerizable monomer used in the present invention having an ether bond and having at least two acryloyl groups at the molecular ends means 20 to 90% by weight of ether in the molecule. With a bond as a repeating unit, a molecular weight of 200-
2000 compounds. For example, ethylene glycol di (meth) acrylate, diethylene glycol (meth)
Acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (with 4 to 23 repeating units of ethylene oxide: 4 repeating units of ethylene oxide)
{For example, trade name; NK ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.} (with 9 repeating units of ethylene oxide)
{For example, trade name; NK ester 9G, manufactured by Shin Nakamura Chemical Co., Ltd.} 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, (having propylene oxide repeating units of 4 to 14), 2,2-bis [4- (methacryloxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) Phenyl] propane, 2,2'-bis [4- (methacryloxypolyethoxy) phenyl] propane (having ethylene oxide repeating units of 9 to 15), trimethylolpropane tri (meth)
Acrylate, tetramethylol methane tetra (meth)
Acrylate or the like is used. Among them, especially 2,2'-
Bis [4- (methacryloxypolyethoxy) phenyl] propane (having 15 repeating units of ethylene oxide) (for example, trade name; NK ester BPE-1300, manufactured by Shin Nakamura Chemical Co., Ltd.) gives a well-balanced cured product property. ,preferable. Here, (meth) acrylate means methacrylate or acrylate. In the present invention, one type of copolymer having an ether bond and having at least two acryloyl groups at the molecular end is usually used, but two or more types may be used.

The amount of the copolymerizable monomer having an ether bond and having at least two acroyl groups at the molecular ends is 100 parts by weight of a prepolymer having at least two unsaturated bonds in the molecule. On the other hand, it is usually 25 to 400 parts by weight. If the amount is less than 25 parts by weight, the copolymerizability of the monomer copolymerizable with the prepolymer is lowered, resulting in poor curing, which is not preferable. On the other hand, when the amount exceeds 400 parts by weight, the elongation percentage of the cured product is improved, but the strength, hot water resistance and corrosion resistance are lowered.

The amount of the copolymerizable monomer having an ether bond and having at least two acroyl groups at the terminal of the molecule is the prepolymer having at least two unsaturated bonds in the molecule, and , 3 to 200 per 100 parts by weight of a resin composed of a monomer copolymerizable with a prepolymer.
Parts by weight. If the amount is less than 3 parts by weight, the elongation of the cured product is not improved and cracks occur during curing. On the other hand, if it exceeds 200 parts by weight, the strength, hot water resistance and corrosion resistance are deteriorated.

Further, the inorganic flakes used in the present invention are materials such as glass, mica, carbon, metal and metal oxide, and have a thickness of 1 to 10 μm and a size of 100 to 5000 μm.
Shows a disk-shaped or plate-shaped solid having a diameter (or major axis) of. 25 to 400 parts by weight of a copolymerizable monomer having an ether bond and having at least two acryloyl groups at the molecular ends, based on 100 parts by weight of a prepolymer having at least two unsaturated bonds in the molecule. The amount of the inorganic flakes is usually 5 to 100 parts by weight with respect to 100 parts by weight of the resin containing. If the amount is less than 5 parts by weight, the corrosion resistance is lost, and if it exceeds 100 parts by weight, the viscosity becomes too high and the workability deteriorates, and the degree of freedom of the inorganic flakes in the lining layer is lost, and the lining layer becomes On the other hand, it becomes difficult to line them up horizontally, which rather reduces the corrosion resistance.

Further, a prepolymer having at least two unsaturated bonds in the molecule and 100 parts by weight of a resin composed of a monomer copolymerizable with the prepolymer have an ether bond and a molecule. The amount of the inorganic flakes is usually 5 to 100 parts by weight based on 100 parts by weight of the resin containing 3 to 200 parts by weight of the copolymerizable monomer having at least two acryloyl groups at the ends. It is a department.
If the amount is out of this range, the same inconvenience as in the above case occurs, which is not preferable.

As described above, a prepolymer having at least two unsaturated bonds in the molecule, or a prepolymer having at least two unsaturated bonds in the molecule and a monomer which can be copolymerized with the prepolymer A resin for flaking which comprises a body and contains an effective amount of a copolymerizable monomer having an ether bond and having at least two acryloyl groups at the molecular ends, with respect to a resin containing an effective amount of inorganic flakes. The composition gives a cured product having improved elongation and good corrosion resistance and crack resistance while maintaining toughness and hot water resistance.

[0017]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. In the following, "part" and "%" are based on weight. Production Example 1 126 parts of fumaric acid and 412 parts of 2,2′-di (4-hydroxypropoxyphenyl) propane were esterified by a usual method to obtain a prepolymer.

Production Example 2 380 parts of an epoxy compound (Epicoat # 828: trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) and 86 parts of methacrylic acid were subjected to an addition reaction by a usual method to obtain a prepolymer.

Production Example 3 The prepolymer obtained in Production Example 1 was diluted with styrene to adjust the styrene content to 40% of the whole to obtain a resin.

Production Example 4 The prepolymer obtained in Production Example 2 was diluted with styrene to adjust the styrene content to 40% of the whole to obtain a resin.

Production Example 5 146 parts of adipic acid, 98 parts of maleic anhydride and 152 parts of propylene glycol were esterified by a usual method to obtain a prepolymer. The prepolymer was diluted with styrene and adjusted so that the styrene content was 40% of the whole to obtain a resin.

Examples 1 to 8 The specific prepolymers or resins obtained in Production Examples 1 to 5 were blended with NK ester in the formulations shown in Table 1 (Table 1), Table 2 (Table 2) and Table 3 (Table 3). BPE-1300, NK ester 4G, NK ester 9G (all three types were trade names, manufactured by Shin-Nakamura Chemical Co., Ltd.), and glass flakes (manufactured by Nitto Boseki Co., Ltd.) were mixed. 6% cobalt naphthenate based on 100 parts of these resin compositions
0.5 parts and 55% methyl ethyl ketone peroxide
1.0 part was added to obtain a mixture. Next, a square box (without lid, metal, 300 × 300 × 300 mm ³ , thickness 10 mm)
The mixture was lined on the inside with a thickness of 2 mm and cured. For this lining molded product, evaluate the corrosion resistance, crack resistance and lining property by the following method,
The results are shown in Table 4 (Table 4). -Corrosion resistance: Various chemicals were added to the lining molded product, and the maximum operating temperature was visually confirmed. ◎: High temperature (70-100 ℃) can be used, ○: Medium temperature (40-70)
℃) Usable △: Usable at normal temperature (40 ° C or less), ×: Unusable ・ Crack resistance and lining property: Cracks and peeling at the corners of the lining molded product were visually confirmed. ◯: No crack and peeling, ×: Crack and peeling

Comparative Examples 1 to 9 Resin compositions were prepared according to the formulations shown in Table 1 (Table 1) and Table 2 (Table 2), and the same operation as in Examples was carried out to obtain lining molded products. Each of the obtained molded products was evaluated for corrosion resistance, crack resistance and lining property by the same method as in Examples, and the results are shown in Table 4 (Table 4).

[0024]

EFFECTS OF THE INVENTION Lining moldings molded using the resin composition according to the present invention have excellent crack resistance and lining properties during molding and curing, and also have good corrosion resistance to chemicals such as acids and alkalis. ..

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuo Chikauchi 1900 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. A copolymerizable monomer having an ether bond and having at least two acryloyl groups at a molecular end, based on 100 parts by weight of a prepolymer having at least two unsaturated bonds in the molecule. A resin composition for flaking, comprising 5 to 100 parts by weight of inorganic flakes per 100 parts by weight of a resin containing 25 to 400 parts by weight. 2. A prepolymer having at least two unsaturated bonds in the molecule, and an ether bond with respect to 100 parts by weight of a resin composed of a monomer copolymerizable with the prepolymer and having a molecule. 5 to 10 parts of inorganic flakes per 100 parts by weight of a resin containing 3 to 200 parts by weight of a copolymerizable monomer having at least two acryloyl groups at its ends.
A resin composition for flaking, comprising 0 part by weight.