JPS5850251B2 - Kakiyouhouhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for crosslinking at room temperature a hydrophilic acrylic copolymer containing 10 to 60% by weight of an ethylenically unsaturated monomer having a tertiary amine group as a functional group. It is.

Acrylate or methacrylate polymers having hydroxyl groups as side chains are insoluble in water despite being hydrophilic polymers.

Therefore, by utilizing this hydrophilic property, by coating the surface of an article made of another substance with the polymer, the surface of the article can be made hydrophilic.

However, this polymer alone has very low strength when it absorbs water, and if you rub the painted surface with your fingers, it will crumble and peel off immediately.

Therefore, when using this polymer, ammonium, lithium, potassium or sodium salts of chromic acid or dichromate, or other strong oxidizing agents,
For example, solid titanates such as tetrapropyl titanate, tetrabutyl titanate, etc. in amounts of 0.2-0.5% have been used.

However, although these are said to be able to be used at room temperature, in reality they require the use of light as an accelerator, heating, or long-term standing in order to be completely crosslinked. It is.

In order to improve these drawbacks, the present inventors focused on epoxy resins as a result of intensive research.

However, the hydroxyl groups in the polymer to be crosslinked with the epoxy resin do not react with each other when heated, but at room temperature they do not react unless the reaction takes a longer time than the above reaction. There's no benefit to it.

One possible method is to add tertiary amines, such as trimethylaminomethylphenol, which are catalysts for epoxy resins, but although this is useful for curing (crosslinking) epoxy resins, it is difficult to add tertiary amines that are catalysts for epoxy resins. Since it does not contribute to the crosslinking of the polymer mixture, the strength of the film obtained by applying the polymer mixture upon absorption of water is hardly improved, and the addition of a catalyst as a third component is troublesome. New problems arise, such as leaching of the reaction catalyst from the film.

According to the present invention, the ethylenically unsaturated monomer having a tertiary amino group as a functional group is 10 to 60% by weight, and the acrylate or methacrylate having a hydroxyl group is 30 to 60% by weight.
At least one copolymer selected from the group consisting of bisphael type, novolac type, and tetrahydroxyphenylmethane type, with 90% by weight and the remainder consisting of other copolymerizable monomers, has an epoxy group at the end of the molecule. The above-mentioned drawbacks were solved by reacting an epoxy resin having two or more of the above at room temperature.

As the ethylenically unsaturated monomer having a tertiary amino group constituting the copolymer in the present invention, (wherein, R1 is a hydrogen atom or a methyl group, and R2 has a carbon atom number of 1
-12, and R3 and R4 are alkyl groups having 1 to 12 carbon atoms.

), there are acrylates or methacrylates with
It is weighed 1:10-60% by weight in the copolymer.

Examples include dimethylaminomethyl acrylate, diethylaminomethyl acrylate, di-n-propylaminomethyl acrylate, diisopropylaminomethyl acrylate, di-n-butylaminomethyl acrylate, diisobutylaminomethyl acrylate, di-n-butyl Aminoethyl acrylate, diethylaminoethyl acrylate, dioctylaminomethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, di-n-propylaminoethyl acrylate, diisopropylaminoethyl acrylate, di-n-butylaminoethyl acrylate, diisobutylaminoethyl acrylate, Diethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylamine-n-propyl acrylate, diethylamino-n-propyl acrylate, di-n-propylamino-n-propyl acrylate, diisopropylamino-n-propyl acrylate, dimoxylamino-n-propyl Acrylate, dimethylaminoisopropyl acrylate, diethylaminoisopropyl acrylate, di-n-propylaminoisopropyl acrylate, dibutylaminoisopropyl acrylate, dimethylamino-n-butyl acrylate, diethylamine-n-butyl acrylate, di-n-butylamino-n -Butyl acrylate, diisobutylamino-n-butyl acrylate, dimethylaminoisobutyl acrylate, diethylaminoisobutyl acrylate, dimethylaminopentyl acrylate, diethylaminooctyl acrylate, dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, di-n-propylaminomethyl methacrylate, diisopropylamino Methyl methacrylate, di-n-butylaminomethyl methacrylate, diisobutylaminomethyl methacrylate, di-5ec-butylaminomethyl methacrylate, dioctylaminomethyl methacrylate,
Dimethylaminoethyl methacrylate, diethylamine ethyl methacrylate, di-n-propylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, di-n-butylaminoethyl acrylate, diisobutylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylamino-n-propylacrylate, diethylamino -n-propyl methacrylate, di-n-propylamino-n-propyl methacrylate, diisopropylamino-n-propyl methacrylate, dipentylamino-n-propyl methacrylate, dimethylaminoisopropyl methacrylate, diethylaminoisopropyl methacrylate, di-n-propylamino Isopropyl methacrylate, dibutylaminoisopropyl methacrylate, dimethylamino-n
-butyl methacrylate, diethylamine-n-butyl methacrylate, di-n-butylamino-〇-butyl meccrylate, diisobutylamino-n-butyl methacrylate, dimethylaminoisobutyl methacrylate,
Examples include diethylaminoisobutyl methacrylate, dimethylaminopentyl methacrylate, and diethylaminooctyl methacrylate.

The acrylate or methacrylate having a hydroxyl group constituting the above-mentioned copolymer includes (wherein, R5 is a hydrogen atom or a methyl group, and R6 is a carbon atom having 2 carbon atoms.
an alkylene group having ~6, m is an integer of 0 to 1,
Moreover, n is O-14.

), which are present in the copolymer in an amount of 30 to 90% by weight.

Examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, tetraethylene glycol monoacrylate, dipropylene Recol monoacrylate, tripropylene glycol monoacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6
-Hydroxyhexyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, triethylene glycol monoacrylate, and the like.

Furthermore, the copolymerizable monomers contained as a remainder in the copolymer include ethylenically unsaturated monomers other than those mentioned above.

For example, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 5eC-butyl acrylate, 2-
Alkyl acrylates such as ethylhexyl acrylate, methyl methacrylate, ethyl meccrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 5ec-butyl methacrylate, 2-ethylhexyl methacrylate,
Alkyl methacrylates such as lauryl methacrylate, cyclohexyl acrylate, acrylonitrile, mecrylonitrile, acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-methylmethacrylamide, N-ethylmethacryl unsubstituted or N-amide, such as N-propyl methacrylamide, etc.
alkyl-substituted acrylamide or methacrylamide,
Aminoalkyl acrylates such as diacetone acrylamide, 2-aminoethyl acrylate, 3-aminopropyl acrylate, 4-aminobutyl acrylate, etc., aminoalkyl such as 2-aminoethyl acrylate, 3-aminopropyl methacrylate, 4-aminoethyl acrylate, etc. Examples include methacrylate, vinyl acetate, and styrene.

The copolymer of the present invention can be obtained by any method such as casting syrup or by bulk polymerization to obtain a polymer and dissolving it in an appropriate solvent, or by solution polymerization or suspension polymerization in a solvent. The following method is adopted.

Polymerization is carried out in the presence of a radical polymerization catalyst, usually at 50 to 14
It is carried out at a temperature of 0°C, preferably 60-120°C, for 1-20 hours, preferably 9-12 hours.

Examples of radical polymerization catalysts include tert-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, methyl ethyl ketone peroxide,
Examples include cumene hydroperoxide, dicumyl peroxide, and abbisisobutyronitrile.

The intrinsic viscosity [η] of the thus obtained copolymer measured using a capillary viscometer is 0.1 to 1.5, preferably 0.35 to 1.0.

The epoxy resin having two or more epoxy groups at the end of the molecule used as a curing agent is an epoxy resin having at least one epoxy group at each end of the molecule, and this is the copolymer 100. To the weight part, 3
~100 parts by weight are used, preferably 5 to 50 parts by weight, most preferably 10 to 30 parts by weight.

For example, bisphenol A is a typical example.
A standard epoxy resin in which epichlorohydrin is reacted at the terminal end of n is 0 or more (trade name, Epicor) 8
28゜Epicoat 827, Epikot 1004 and Epicoat 1009, manufactured by Shell Chemical Co.) or novolak type products with n of 1 or more (trade name, Epicoat 152, manufactured by Shell Chemical Co.), or with two or more epoxides attached to the end. (trade name, Epon 1031, manufactured by Shell Chemical Co., Ltd.) and 4,4-diaminodiphenylpropane tetraglycidyl ether.

The composition thus obtained is usually applied from an organic solvent solution to the surface of the structure to be painted.

Suitable solvents include lower alcohols such as methanol, ethanol, propatool, isopropanol, butanol, etc., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc. Ethylene glycol monoalkyl ether, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. alone or in mixtures of two or more, and mixtures of these solvents with water and water, and in some cases. Aromatic and aliphatic hydrocarbons, such as benzene, toluene, xylene and hexane, or petroleum-based mixed solvents can also be used.

The coating of the present invention is a contaminant-visible material that has been previously applied to the surface of an underwater structure protected by a corrosion-resistant topcoat, such as a paint based on an epoxy resin, a vinyl resin, or a chlorinated rubber. Demonstrates sufficient adhesion to painted and unsaturated polyester resin-glass fiber laminates.

The thickness of the coating applied will vary depending on the particular composition used and the method of application.

The thickness is usually 10 to 500μ, preferably 30μ
~200μ.

The coating is applied to the surface of the object by any method such as brushing, dipping, spraying, or rolling.

The coating coated in this manner is dried at room temperature for 3 to 20 hours, preferably 5 to 10 hours, to complete the crosslinking reaction.

Of course, heating can also be used to speed up the crosslinking time.

The coating thus obtained is water-insoluble and has a water absorption rate of 10 to 100% by weight, preferably 25 to 80% by weight.
Weight at the weight clerk.

In order to keep the underside of ships clean, the hydrophilic polymer compositions of the present invention can be applied over conventional antifouling agents, provided they have sufficient permeability.

To provide a coating that prevents fouling by marine life,
Any conventional inorganic or organic antifouling agent may be mixed into the coating composition of the present invention, including cuprous oxide, copper powder, mercuric oxide, ferrous oxide, etc. - Commonly used compounds such as copper mercuric monoxide, organic tin compounds, and organic lead compounds can be used.

The resist agent is releasably incorporated into the hydrophilic polymer coating.

The amount of antifouling agent required during coating will vary depending on the particular agent used and the degree of fouling encountered in the particular application of the coated underwater structure; The antifouling agent ranges from 2 to 200% by weight based on solids, but small amounts such as 0.1% by weight can also be used.

The amount of antifouling agent should not be added so as to prevent the hydrophilic polymer from forming a continuous coating.

Of course, the usual pigments and fillers can also be mixed into the composition, such as titanium dioxide, red lead, iron oxide, talc, aluminum silicate, acid clay, pumice, zinc oxide, calcium carbonate, aluminum powder, etc. .

As described above, according to the present invention, since the copolymer contains an ethylenically unsaturated monomer having a tertiary amine group as a functional group and an acrylate or methacrylate having a hydroxyl group in a specific ratio, Epoxy resins having two or more epoxy groups at the ends of their molecules can be cured at room temperature.

Therefore, in the past, even if the coating could be applied, it was either virtually impossible to cross-link and cure, or even if it was possible, it took a long time because the cross-linking and curing reaction required heating or light irradiation. It has the advantage that it can be cross-linked and cured at room temperature even when it is applied to large products such as the bottoms of ships such as motorboats, steamers, tankers, warships, and other static underwater structures.

Moreover, the crosslinking does not substantially reduce its water absorption, so when it is painted on the bottom of a ship, its water absorption reduces water resistance, greatly contributing to fuel savings and speeding up.

Next, the present invention will be explained in more detail with reference to Examples.

In addition, in the following examples, all terms mean % by weight unless otherwise specified.

Example 1 Capacity 1010 with thermometer, reflux condenser and stirrer
90 g of 2-hydroxyethyl methacrylate, 10 g of dimethylaminoethyl methacrylate, and 400 g of ethylene glycol monomethyl ether as a solvent were supplied to a 0O three-bottomed flask, and azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added as a polymerization catalyst.

) was added at a concentration of 3% based on monomer, and polymerization was carried out at 80° C. for about 8 hours to obtain a syrup-like copolymer solution.

The intrinsic viscosity [η] of the obtained copolymer was 0.5 as measured by capillary viscometry.

Take 100 g of the copolymer solution obtained in this way,
To this was added 1 g of an epoxy resin obtained by reacting epichlorohydrin with the terminal end of bisphenol A (trade name: Epicoat 828, manufactured by Shell Chemical Co., Ltd.) and stirred well. ) on an aluminum disc coated with a thickness of 50μ,
A further topcoat was applied to obtain a coating approximately 30 microns thick.

This disk was left at room temperature for 12 hours to completely cure the crosslinking, and then immersed in water and rotated at 2,400 rpm for 50,000 hours, but the coating did not peel off at all and no abnormalities were observed.

Further, the water absorption rate of this coating was about 60%.

Comparative Example 1 To the copolymer solution obtained by the method of Example 1, 20 g of an aqueous solution of ammonium dichromate was added so that the ratio of ammonium dichromate to the copolymer was 2 parts, and the mixture was thoroughly stirred. When the coating was applied to a disc in the same manner as in Example 1, left at room temperature for 12 hours, and then immersed in water, the coating immediately swelled and peeled off from the surface of the underlying paint.

Comparative Example 2 A 20% aqueous solution of ammonium dichromate was added to the copolymer solution obtained by the method of Example 1 so that the ratio of ammonium dichromate to the copolymer was 10%, and the mixture was thoroughly stirred. The solution was applied to a disk in the same manner as in Example 1, and left at room temperature for 72 hours.

When this product was immersed in water, it did not swell immediately as in Comparative Example 1, but at 2400 rpm
After being rotated for a period of time, most of the coating had peeled off from the surface of the base paint, and the remaining coating was mushy and easily torn when rubbed with a finger.

Comparative Example 3 A copolymer solution containing ammonium dichromate obtained by the method of Comparative Example 1 was applied to a disk in the same manner as in Example 1, and a mercury lamp (with a powder of ultraviolet light (300 to 450 nm)) was applied. Approximately 40C using Toshiba Eye Black Light)
The coating was irradiated for about 12 hours at room temperature from a distance of rn.

The coating thus obtained was strong even when immersed in water, and did not peel off as in Example 1 even when rotated at 2400 rpm for 500 hours.

Example 2 Epikote 1009 (manufactured by Shell Chemical Co., Ltd.) as a curing agent was added to the copolymer solution obtained by the method of Example 1 in an amount of 10% based on the copolymer in the solution, and the mixture was stirred. was applied to a disc in the same manner as in Example 1, and then left at room temperature for 12 hours.

When this product was tested in the same manner as in Example 1, the strength of the coating was almost the same as in Example 1, and the water absorption rate was 40%.

Example 3 80 g of 2-hydroxyethyl methacrylate, 20 g of diethylaminoethyl methacrylate and 400 g of ethylene glycol monomethyl ether were fed into a reaction flask similar to that in Example 1, and AIB was added as a polymerization catalyst.
0.5φ of N was added to the monomer, and polymerization was carried out at a temperature of 75° C. for about 10 hours to obtain a syrup-like copolymer solution.

Intrinsic viscosity of the obtained copolymer measured by capillary viscosity measurement [
η] was 0.7.

Example 1 After adding Epon 1031 (manufactured by Shell Chemical Co., Ltd.) as a curing agent to the copolymer solution obtained in this manner so as to give a concentration of 10% based on the copolymer in the solution and stirring well. It was applied to a disk prepared with a base treatment in the same manner as above and left at room temperature for 12 hours.

When this was tested in the same manner as in Example 1, the strength of the coating was as good as in Example 1, and its water absorption rate was about 50%.

Example 4 In a reaction flask similar to Example 1 were added 2-hydroxyethyl methacrylate 6 (1, 12 g dimethylaminoethyl methacrylate and 38 g diacetone acrylamide).
Furthermore, 400 g of ethylene glycol monomethyl ether was supplied as a solvent, and AIBN was added as a polymerization catalyst.
o, 5& were added and polymerization was carried out at a temperature of 800C for 10 hours to obtain a syrupy copolymer solution.

Intrinsic viscosity of the obtained copolymer measured by capillary viscosity measurement [
η] was 0.8.

Example 1 After adding Epon 1031 (manufactured by Shell Chemical Co., Ltd.) as a curing agent to the copolymer solution thus obtained in an amount of 20% of the copolymer in the solution and stirring well. A film thickness of 30 μm was applied to a disc prepared in the same manner as above and left at room temperature for 12 hours.

This disc was immersed in water and rotated at 2400 rpm for 500 hours, but the coating was in good condition.
It had sufficient strength even when rubbed with fingers, and its water absorption rate was about 80%.

Comparative Example 4 A 20% solution of ammonium dichromate was added to the copolymer solution obtained by the method of Example 4 so that the ratio of ammonium dichromate to the copolymer was 5%, and the mixture was thoroughly stirred. Coat it on a disk in the same manner as in Example 4, and apply it at room temperature to 72
When it was left to stand for a while and then immersed in water, the coating immediately swelled and peeled off from the surface of the underlying paint.

Comparative Example 5 A 20% solution of ammonium dichromate was added to the copolymer solution obtained by the method of Example 4 so that the ratio of ammonium dichromate to the copolymer was 5%, and the mixture was thoroughly stirred. After applying it to a disk in the same manner as in Example 4, it was heated at room temperature for 12 hours using a mercury lamp as in Comparative Example 3.

When the coating thus obtained was immersed in water, it immediately swelled and peeled off from the substrate.

Comparative Example 6 100 g of 2-hydroxyethyl methacrylate and 400 g of ethylene glycol monomethyl ether were fed into a reaction flask similar to Example 1, and AIBNO
, :l was added and polymerization was carried out at a temperature of 75°C for 10 hours to obtain a syrupy copolymer solution.

Copolymer solution thus obtained 100. ! After adding 1 g of Epicor) 828 (manufactured by Shell Chemical Co., Ltd.) and 0.1 g of trimethylaminomethylphenol to i' and mixing well, it was coated on a disk in the same manner as in Example 1, and 1 g was added at room temperature.
After being left for 2 hours, the coating immediately swelled and peeled off from the underlying surface when it was immersed in water.

Example 5 Dimethylaminoethyl methacrylate 5 (30 g of 1,2-hydroxyethyl methacrylate, 10 g of lauryl methacrylate, 10 g of methacrylic acid and 400 g of methyl cellosolve as a solvent were supplied to the same flask as in Example 1, and azobis as a polymerization catalyst was supplied. Add 0.9.9% of isobutyronitrile and carry out 10 polymerizations at 80°C,
A syrupy copolymer solution was obtained.

Epon 1031 (manufactured by Shell Chemical Co., Ltd.) as a curing agent was added to the copolymer solution obtained in this way at a concentration of 20% based on the copolymer in the solution and stirred well. A layer of 30 .mu.m thick was coated on a similarly prepared disc and left at room temperature for 12 hours.

This disk was immersed in water at 240 Or, p, m, 5
It was rotated for 00 hours, but the coating was in good condition.
Moreover, it had sufficient strength even when rubbed with fingers.

The water absorption rate of this coating was approximately 120 parts.

Example 6 In a flask similar to Example 1, 50 g of dimethylaminoethyl methacrylate, 20 g of diacetone acrylamide,
30.9 g of 2-hydroxyethyl methacrylate and 40 M of methyl cellosolve were supplied as a solvent, and 0.5 g of azobisisobutyronitrile was added as a catalyst, followed by reaction at 75° C. for 10 hours.

Epon 1031 (manufactured by Shell Chemical Co., Ltd.) as a curing agent was added to the copolymer solution obtained in this manner in an amount of 20 ml per copolymer in the solution, and after stirring well, the same procedure as in Example 1 was carried out. It was applied to a disc with a base treatment of 30 μm in thickness and left at room temperature for 12 hours.

When this disk was rotated in water at 240 Or, p, m for 500 hours, peeling occurred in some places.

The water absorption rate at this time was 15o.

Therefore, when we conducted a similar test with twice the amount of hardening agent (40%), we found that the coating was in good condition after 500 hours of rotation in water, and had sufficient strength even when rubbed with fingers. Was.

At this time, the water absorption rate had decreased to 80%.

Example 7 In a flask similar to Example 1, 40 g of dimethylaminoethyl methacrylate and 3 (1
, 30 g of 2-hydroxyethyl methacrylate and 400 g of methyl cellosolve were added, and 0.5 g of abbisisobutyronitrile was added as a catalyst.
The mixture was allowed to react for 10 hours.

Epon 1031 (manufactured by Shell Chemical Co., Ltd.) as a curing agent was added to the copolymer solution thus obtained in an amount of 20 parts to the copolymer in the solution and stirred well. It was applied to a disc with a similar surface treatment to a film thickness of 30 μm and cured at room temperature for 12 hours.

When this disk was rotated in water at 240 Or-p-m for 500 hours, peeling occurred at the periphery as in Example 7, so Epon 1031 (manufactured by Shell Chemical Co., Ltd.) was similarly
When we examined it, we found that it did not show any abnormalities even after being rotated in water for 500 hours, and had sufficient strength even when rubbed with one's fingers.

Claims (1)

[Claims] 1 (a) 10 to 60% by weight of an ethylenically unsaturated monomer having a tertiary amino group as a functional group, (b) acrylate or methacrylate having a hydroxyl group -130% by weight
~90% by weight and (c) at least one selected from the group consisting of bisphenol type, novolac type and tetrahydroxyphenylmethane type, and A method for crosslinking a hydrophilic copolymer, which comprises reacting with an epoxy resin having two or more epoxy groups at the terminals of one type of molecule.