JPH05230160A - Composition suitable for lining - Google Patents

Abstract

PURPOSE:To provide a composition, excellent in film drying properties and adhesion to substrates and suitable for low-malodor linings with hardly any malodor in lining. CONSTITUTION:The objective composition suitable for lining is obtained by blending (1) 10-70wt.% urethane-acrylate having at least one (meth)acryloyl group in one molecule with (2) 10-80wt.% monomer having >=150 molecular weight and (meth)acryloyl group and (3) 2-20wt.% polyallyl ether having at least two allyl ether groups in one molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition suitable for lining in fields requiring a coating film thickness thicker than conventional solvent-based linings, such as heavy-duty anticorrosion linings. To a composition suitable for a low odor lining, which has a low or almost no odor.

[0002]

2. Description of the Related Art Conventionally, epoxy resins, polyurethane resins, etc. have been typically used as lining resins, but all of these existing resins have a high viscosity and are used in a form dissolved in a solvent. .. In addition to these solvent-based lining materials, in the lining materials using polyester resin and vinyl ester resin, the monomer used in combination also serves as a solvent, and the coating film is different from general solvent-based lining materials and is 100% solidified. However, the use of monomers is still indispensable. Thus, in any case, the conventional lining materials cannot avoid the odor of the solvent or the monomer at the lining construction site.

In recent years, due to environmental problems, there has been a remarkable movement to avoid the use of such odorous components as solvents and monomers as much as possible, but it has been a very difficult problem.

As a result of addressing this problem and making efforts to solve the problem, the inventors of the present invention have a strong anaerobic curing property, and a urethane-containing compound having at least one (meth) acryloyl group in one molecule.
In a combination system with an acrylate and a monomer having a (meth) acryloyl group having a high boiling point and a molecular weight of 150 or more, by using an appropriate amount of a polyallyl ether having at least two allyl ether groups in one molecule, The present invention has been completed by finding that the surface of the coating film becomes non-adhesive even when a thin film such as a lining is cured together with the organic acid salt of cobalt.

That is, according to the present invention, (1) 10-70% by weight of a urethane-acrylate having at least one (meth) acryloyl group in one molecule, (2) a molecular weight of 150.
Monomers 10 having the above (meth) acryloyl group
80% by weight, (3) a composition suitable for lining, which comprises the combined use of 2 to 20% by weight of a polyallyl ether having at least two allyl ether groups in one molecule.

The urethane-acrylate having at least one (meth) acryloyl group in one molecule of the component (1) used for preparing the composition of the present invention is, for example, (a) a terminal hydroxyl group. A group of polyethers having a molecular weight (number average, the same applies hereinafter) of about 1,000 to 3,000 is reacted with an unsaturated isocyanate, and (b) a terminal is a hydroxyl group, a molecular weight of 1,000 to 3, 0
It can be synthesized by reacting a polyester of about 00 with an unsaturated isocyanate, and reacting an unsaturated monoalcohol having a (meth) acryloyl group with a diisocyanate.

[0007] Unsaturated isocyanates include isocyanate ethyl methacrylate (the following formula) in the form of sharing an isocyanate group and a (meth) acryloyl group.

[Chemical 1] Alternatively, a 1: 1 reaction between a hydroxyl group and an isocyanate group of an unsaturated alcohol having a (meth) acryloyl group and a diisocyanate compound may lead to a type in which a (meth) acryloyl group and an isocyanate group are shared. I can give you something. If one of these is shown, it is as in the following formula.

[Chemical 2] In this case, the two isocyanate groups have different reactivities,
For example, it is convenient to use 2,4-tolylene diisocyanate or isophorone diisocyanate.

The monomer (2) having a (meth) acryloyl group having a molecular weight of 150 or more, which is used for preparing the composition of the present invention, has a high boiling point, a low odor, and a low molecular weight. Those having a boiling point of less than 150 have a low boiling point and have a significant odor, and are not preferably used. The following types are typical examples of the component (2).

(I) A compound obtained by adding a monoepoxide, for example, an alkylene monoepoxide to a phenol, and further esterifying the generated alcoholic hydroxyl group with (meth) acrylic acid can be mentioned. The raw material phenols for synthesizing the monomer having a (meth) acryloyl group having a molecular weight of 150 or more are not particularly limited, but commercially available phenols and substituted phenols can be used. Examples thereof are phenol, p-cresol, m-cresol, various xylenols, p-phenylphenol, p-tertiarybutylphenol, p.
-Ethylphenol, p-isopropylphenol, p
-Examples include octylphenol. Ethylene oxide is the most commonly used alkylene monoepoxide,
Other examples include propylene oxide and epichlorohydrin. Esterification is carried out under organic or inorganic acidic catalysts such as paratoluene sulfonic acid and sulfuric acid, benzene,
It is carried out in the presence of an organic solvent which is distilled off azeotropically with water such as toluene. After the completion of esterification, the target (meth) having a molecular weight of 150 or more is neutralized, washed with water, a solvent, and distilled off.
A monomer having an acryloyl group can be obtained.

In addition to the above, the monomer having a (meth) acryloyl group having a molecular weight of 150 or more used in the present invention is (ii) a monomer synthesized by reacting (meth) acrylic acid with an alkylene monoepoxide. can give. In this case, the resulting monomer will necessarily have secondary hydroxyl groups. In order to reduce the water solubility of the monomer, epichlorohydrin, styrene oxide, cyclohexene monoepoxide, phenylglycidyl ether and the like are desirable as the alkylene monoepoxide. Of these alkylene monoepoxides, the use of epichlorohydrin is most advantageous when cost is also taken into consideration.

The reaction is carried out by mixing (meth) acrylic acid and alkylene monoepoxide and using a reaction catalyst such as a tertiary amine, a quaternary ammonium salt or triphenylphosphine in combination. At this time, it is necessary to use a polymerization inhibitor. As a matter of course, the above (i) and (i
It is possible to mix and use the monomers produced in i), and it is preferable in practical use. However, the above-mentioned urethane-acrylate of the component (1) and the molecular weight of the component (2) of 150 or more are used.
In combination with a monomer having a (meth) acryloyl group,
Due to the anaerobic curability of the (meth) acryloyl group, a curing failure occurs in the presence of air and it cannot be used as a lining material.

In order to solve this drawback, in the present invention, it is necessary to blend, as the component (3), a polyallyl ether having at least two allyl ether groups in one molecule. The polyallyl ether of the component (3) that can be used in the present invention is synthesized by reacting a necessary amount of allyl glycidyl ether in the presence of glycol or trifunctional polyol. In the reaction, a small amount of Lewis acid or its ether, a complex with acetic acid is used,
After the reaction, neutralize, wash with water and dehydrate to obtain the product. The molecular weight of the polyallyl ether is preferably 3,000 or less. 3,000
Although a molecular weight of 0 or more does not cause any particular problem, it is recognized that the higher the molecular weight, the lower the compatibility with the urethane-acrylate. If the compatibility is not a problem, the molecular weight is not particularly limited.

The urethane-acrylate having at least one (meth) acryloyl group in one molecule of the component (1), the monomer having a (meth) acryloyl group having a molecular weight of 150 or more of the component (2), and the component (3). When the total amount of the component (1), the component (2) and the component (3) is 100% by weight, the blending ratio with the polyallyl ether having at least two allyl ether groups in one molecule of 1) Component 10
-70 wt%, (2) component 10-80 wt%, (3) component 2-20 wt%, preferably (1) component 20
To 60% by weight, (2) component 30 to 70% by weight, and (3) component 5 to 15% by weight, and appropriately determined within the above range in consideration of necessary performance such as viscosity, thixotropy-providing property, and air-curing property. Be done. (1) component, (2) component and (3)
If the mixing ratio of the components is outside the above range, the effect of the present invention cannot be obtained. For example, a decrease in the component (3) results in poor air curability. Further, when the component (1) is small, the thixotropy property is reduced and the coating film is liable to sag, while when it is large, the viscosity is high and the coating becomes difficult.

Curing of the composition of the present invention requires the use of an organic acid salt of cobalt in the organic peroxide catalyst.
In order to make the surface of the coating film non-sticky, it is necessary to use an organic acid salt of cobalt in combination with an organic peroxide, and when the amount of the organic acid salt of cobalt is small, for example, the composition If it is 0.1% by weight or less based on the weight of the above, it takes a long time for the surface of the coating film to become non-adhesive, which is not practical. The amount of the organic acid salt of cobalt is preferably 0.3 to 2 parts by weight, more preferably 0.5 to 100 parts by weight of the composition.
~ 1.5 parts by weight. The type of the organic peroxide that is the curing agent is not particularly limited as long as it is a type that undergoes a redox reaction with an organic acid salt of cobalt. In addition, like benzoyl peroxide, the redox reaction does not occur with the organic acid salt of cobalt, but in the system in which a promoter such as aromatic amines is used in combination, the presence of the organic acid salt of cobalt does not affect the coating surface. It functions as an adhesive and is used as an essential component.

Needless to say, the composition suitable for the lining according to the present invention may be used in combination with a filler, a colorant, an ultraviolet absorber, a reinforcing material, a thermoplastic polymer or the like, if necessary at the time of applying the lining.

[0016]

EXAMPLES Examples will be shown below to facilitate understanding of the present invention.

Example 1 (a) Synthesis of unsaturated urethane-acrylate (A) A 1 l separable flask equipped with a stirrer, a reflux condenser, a gas introduction tube, and a thermometer was charged with polypropylene glycol having a molecular weight of about 2,500. When 500 g, 32 g of isocyanate ethyl methacrylate and 0.5 g of dibutyltin dilaurate were added and reacted at 65 to 70 ° C. for 5 hours, infrared analysis showed that the isocyanate group had disappeared. An almost colorless syrup-like unsaturated urethane-acrylate (A) was obtained.

(B) Synthesis of polyallyl ether (I) In a 1 liter separable flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, 175 g of toluene, 32 g of ethylene glycol, boron trifluoride ether adduct 1 g was charged, and 316 g of allyl glycidyl ether was gradually added dropwise. While cooling, the temperature was kept at 40 ° C. or higher, the temperature was raised to 65 to 70 ° C. after the completion of dropping, and the temperature was maintained for 5 hours. Then, after washing with a 3% sodium carbonate solution, it was washed twice with water, and toluene was distilled off under reduced pressure (20 to 30 Torr). Polyallyl glycidyl ether (I) having a molecular weight of about 1,300 was obtained in an almost colorless syrup form.

Production of lining material (a) Unsaturated urethane-acrylate (A) 32 parts by weight Polyallyl glycidyl ether (I) 8 parts by weight p-cresol-ethylene oxide adduct acrylic acid ester (manufactured by Soken Chemical Industry Co., Ltd., I-1612) Dissolve 60 parts by weight uniformly, and further add 40 parts by weight of talc 1 part by weight of erogen, antifoaming agent (silicone type) 10 ppm 0.7 parts by weight of cobalt octylate (8% Co) to make it uniform. It was stirred with a disper for 20 minutes. After standing overnight, a lining material (a) having a light reddish brown color and a viscosity of about 51 poise was obtained.

A composition in which 100 parts by weight of the lining material (a) and 1.5 parts by weight of methyl ethyl ketone peroxide were uniformly mixed was coated on a bonderite steel plate with a bar coater to a thickness of 0.2 m / m. The coating film was completely left non-tacky after standing overnight (18 to 23 ° C.), and the adhesiveness to the cross stitch was 100/100 and the hardness was F. But,
The coating film obtained by applying the composition prepared by the same composition except that the polyallyl glycidyl ether (I) was removed from the lining material (a) under the same conditions as above was sticky even after standing for 1 week, No dry coating was obtained. The lining material (a) is almost odorless, but suitable fragrance,
For example, by adding ethyl vanillin, linalool, β-phenylethyl alcohol and the like in an amount of 0.01 to 0.001 phr, it is possible to make them practically odorless.

Example 2 Synthesis of Unsaturated Urethane-Acrylate (B) ( Synthesis of Hydroxy Polyester) 2-Methylpropanediol was placed in a 1-liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas introduction tube. 1, 3 to 30
0 g, dimethyl terephthalate 291 g, zinc acetate 1.
5 g was charged, and at the stage when the outflow of methanol was completed at 160 to 180 ° C., 219 g of adipic acid was further added, and esterification was carried out at 200 to 205 ° C. in a nitrogen stream to obtain an acid value of 6.1.
(Molecular weight about 2,600), then hydroquinone 0.
05 g was added and dissolved in 550 g of phenoxyethyl methacrylate at a temperature of 120 ° C. A hydroxypolyester having a viscosity of about 640 poise was obtained in a light tan color.

(Synthesis of unsaturated isocyanate) Stirrer,
A 1 liter separable flask equipped with a reflux condenser, a thermometer and a dropping funnel was charged with 174 g of 2,4-tolylene diisocyanate, 0.03 g of parabenzoquinone and 318 g of phenoxyethyl methacrylate, and after replacement with dry nitrogen, the temperature was adjusted to 65 to 70 ° C. While maintaining the temperature, 144 g of hydroxypropyl methacrylate was added dropwise. After the dropping is completed, the temperature is kept at the same temperature for 1 hour, and then 0.5 g of dibutyltin dilaurate is added.
The mixture was kept at 60 ° C. for another hour. As a result of infrared analysis,
It was confirmed that the hydroxyl group disappeared and the isocyanate group was almost halved. The obtained unsaturated isocyanate (the following structural formula) (50% phenoxyethyl methacrylate solution) was obtained as a pale yellowish brown liquid.

[Chemical 3] Into a 1 liter separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas introduction tube, 600 g of hydroxyl polyester and 160 g of unsaturated isocyanate were added, and the reaction was carried out at a temperature of 70 to 75 ° C. for 3 hours. As a result, it was confirmed that the isocyanate group disappeared.
Furthermore, 480 g of phenoxyethyl methacrylate was added, and unsaturated urethane-acrylate (B) (solid content about 3
0%) was obtained with a viscosity of 8.1 poise and a pale tan color.

Synthesis of allyl ether oligomer (II) In a 1-liter separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a separating funnel, 254 g of trimethylolpropane diallyl ether, 176 g of toluene, and boron trifluoride ether were added. 0.7 g of the product was charged, and 570 g of allyl glycidyl ether was added dropwise while cooling so as not to exceed 40 ° C. After completion of the dropping, the mixture was heated at 60 to 65 ° C. for 5 hours, washed in the same manner as in Example 1, and toluene was distilled off to obtain an almost colorless syrup-like allyl ether oligomer (II) having a molecular weight of 800 to 850.

A kneading lining material (b) was produced with the following formulation. Unsaturated urethane-acrylate (B) 30 parts by weight Phenoxyethyl methacrylate 60 parts by weight Allyl ether oligomer (II) 10 parts by weight # 325 Glass flakes (manufactured by Nippon Glass Fiber Co., Ltd.) 30 parts by weight Erosil 2 parts by weight Cobalt octylate 1 part by weight Kayaku Akzo Co., Ltd., trade name 328EM 2 parts by weight

The above lining material (b) was coated on Bonderite steel to a thickness of 200 μm. After being left overnight, the coating film is completely hardened to the surface and the surface hardness is 2H.
Met. Further, even if this steel sheet was bent 90 °, no cracking or peeling of the coating film was observed. However, in the lining material (b), the allyl ether oligomer (I
The coating film prepared by applying the composition prepared in the same formulation except that the above I) was applied under the same conditions as above had a tacky surface even after standing overnight.

Example 3 Synthesis of Urethane-Acrylate (C) Epichlorohydrin 3 was placed in a 1 liter separable flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel.
70 g, triethylamine 3.5 g, and hydroxin 0.2 g were charged, and methacrylic acid 3 was added at 110 to 115 ° C.
44 g was added dropwise over 30 minutes. 12 during heating during dropping
When the temperature is maintained at 5 to 130 ° C. and the reaction is performed for 5 hours after the dropping,
The acid value became substantially zero. Under a reduced pressure of 3 to 5 Torr, unreacted substances were distilled off at 70 to 80 ° C. to obtain a pale yellow epichlorohydrin-methacrylic acid adduct (1-chloromethyl-2-hydroxypropyl methacrylate). Next, 250 g of diphenylmethane diisocyanate was added, and the mixture was reacted at 70 to 75 ° C. for 5 hours. As a result of infrared analysis, it was confirmed that the free isocyanate group had disappeared.
A urethane-acrylate (C) having a light yellowish brown color and a viscosity of 8.2 poise was obtained.

A lining material (c) was produced with the following formulation. Urethane-acrylate (C) 90 parts by weight Polyallyl glycidyl ether (I) manufactured in Example 1 10 parts by weight Talc 30 parts by weight Erosil 1.5 parts by weight Cobalt octylate 1 part by weight Pyrrolidine-acetylacetonate (manufactured by Nippon Emulsifier) , Naxlator P) 0.2 parts by weight Silicon defoamer 10ppm

To 100 parts by weight of the above lining material (c), 2 parts by weight of cumene hydroperoxide was added, and a 100 μm thick coating was applied on a bonderite steel plate. After being left to stand overnight, the coating film was hardened to the surface and had a hardness of F and 100/100 in a goggles adhesion test, indicating good adhesion.

[0029]

The composition of the present invention has a low odor at the time of lining, excellent coating film drying property, and excellent adhesion to a substrate.

Claims (3)

[Claims] (1) Urethane-acrylate 1 having at least one (meth) acryloyl group in one molecule.
0 to 70% by weight, (2) 10 to 80% by weight of a monomer having a (meth) acryloyl group having a molecular weight of 150 or more, (3) a polyallyl ether 2 to 20 having at least two allyl ether groups in one molecule. A composition suitable for lining consisting of the combined use of weight%. 2. The lining according to claim 1, wherein the monomer having a (meth) acryloyl group having a molecular weight of 150 or more is an esterification product of a reaction product of a phenol with a monoepoxide and (meth) acrylic acid. Suitable composition. 3. The composition suitable for a lining according to claim 1, wherein the monomer having a (meth) acryloyl group having a molecular weight of 150 or more is a reaction product of a monoepoxide and (meth) acrylic acid.