JPH0250928B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hydrolyzable resin composition, and more specifically, the present invention relates to a hydrolyzable resin composition, and more specifically, the present invention relates to a hydrolyzable resin composition. (In the formula, R ₁ is hydrogen or a methyl group; l and m are 0 or an integer of 1 to 4; k is 0 or 1; R ₂ is hydrogen, a hydroxyl group, or a methyl group; R ₃ is

[expression] or

A group represented by [Formula]; n is 0 or an integer of 1 to 6; X ₁ is a cyano group, a nitro group, or _a halogen atom;
Relating to a method for producing a hydrolyzable resin composition useful as a resin vehicle for ship bottom paint and having a molecular weight of 3,000 to 50,000 and containing at least 20% by weight of repeating units represented by X ₄ (respectively hydrogen, cyano group, nitro group, or halogen atom) It is. The present inventors discovered that the general formula or (In the formula, R ₁ and R ₂ are hydrogen or methyl groups, m is 0 or an integer of 1 to 6, n is an integer of 1 to 8, X ₁ , X ₂ ,
A polymer or copolymer having one or more halogenated fatty acid bonding units (at least one of which is a halogen and the remainder are halogens or hydrogen) is hydrolyzed in seawater to form CX ₁ X _{2 X 3} (CH ₂ ) _n COOH produces a halogenated fatty acid that has strong bactericidal properties against marine bacteria, and the polymer main chain acquires hydrophilic groups and dissolves in seawater.
It was found to be extremely useful as an antifouling paint vehicle, and a patent application was filed on June 29, 1981 (title of the invention: "Antifouling Paint"). The present invention is based on the above patent application.
This is a further development of the invention of No. 56-101463. In other words, a matrix polymer that is ideal as an antifouling paint vehicle has sufficient strength as a coating film, is moderately hydrolyzed and dissolved in seawater, and is toxic to marine organisms, such as the halogenated fatty acids mentioned above. It emits kimono. However, if the paint film is gradually hydrolyzed and dissolved in seawater, the antifouling agent does not necessarily have to be bound to the polymer; it can be stably eluted over a long period of time even if it is simply mixed in. However, various conventionally known organic or inorganic antifouling agents can be used. Furthermore, paint films are usually rich in very fine irregularities, but if a hydrolyzable resin is used as the film forming agent, hydrolysis will proceed selectively from the convex parts of the paint film in proportion to the number of collisions with water. Over time, the paint film becomes smoother and the frictional resistance of the paint film against water is reduced. When used as a ship bottom paint, this will lead to a significant improvement in fuel efficiency. In this way, in the field of ship bottom coatings, a coating film with sufficient strength is created using normal coating methods, and it does not hydrolyze in a neutral atmosphere, but gradually hydrolyzes at a moderate rate in slightly alkaline seawater. It is highly desirable to provide a polymeric material that undergoes hydrolysis and dissolves, and it is certainly a preferred embodiment that toxic substances for marine organisms are separated and released from the polymeric material as a result of hydrolysis.
It is clear that this is not necessarily essential, but can also be called an incidental requirement. In the first place, for a polymer to be water-soluble, it is necessary to have a certain amount of hydrophilic groups such as hydroxyl groups and carboxyl groups in the polymer molecule, and if the proportion is too large, the resin itself will easily dissolve in water and become water-soluble. It cannot be used as a paint vehicle. Furthermore, since the presence of hydrophilic groups causes swelling and peeling of the resin due to water, it is preferable that the paint vehicle has as few hydrophilic groups as possible. In this way, when trying to create a coating film with sufficient strength after painting and obtain a polymer for ship bottom paint that gradually dissolves in seawater, the dissolution rate should be controlled simply by the proportion of hydrophilic groups in the resin. It is extremely difficult to do so. Therefore, the hydrophilic groups in the resin are appropriately blocked, and do not exhibit hydrophilicity in a normal neutral atmosphere, but are gradually hydrolyzed under specific conditions such as weak alkalinity, resulting in free hydrophilic groups. If we can obtain something that recovers the hydrophilicity and exhibits hydrophilicity, we should be able to achieve the above objective. Therefore, the present inventors investigated the hydrolysis rate of vinyl acetate polymer, which is a polymer having the simplest fatty acid ester bond, and found that the acyloxy groups pendant in the resin do not react at all in neutral or weakly alkaline water. Not subject to change and not hydrolyzed When an electron-withdrawing group (X) such as a halogen atom, nitro group, or cyano group is introduced into the acyl moiety, the electron density of the carboxyl group in the ester bond decreases, making it more susceptible to hydrolysis and not being affected in a neutral atmosphere. Deacylation occurs gradually in slightly alkaline seawater. It has been found that hydroxyl groups are added to the polymer. Furthermore, the elution rate (hydrolysis degree) of the polymer into water is determined by the amount of water contained in the polymer.

The bond concentration of [formula],

Although it depends on the binding energy of [Formula] and the concentration of functional groups such as coexisting OH groups and COOH groups, in order to create a strong coating film, the concentration of free hydrophilic groups is suppressed as much as possible, and the polymer is formed after hydrolysis. It has been discovered that in order to make a polymer water-soluble due to the hydrophilic groups imparted to it, the proportion of such hydrolyzable bonding units must exceed a certain critical value. The present invention has been made based on this knowledge.
That is, according to the present invention, (1) General formula (1) [In the formula, R ₁ is hydrogen or a methyl group; k is 0 or 1; l and m are each 0 or an integer of 1 to 4; R ₂ is hydrogen, a hydroxyl group, or a methyl group; R ₃
teeth

[expression] or

[Formula]; n is 0 or an integer _of 1 to 6; X _{1 is} a cyano group, a nitro group, or a halogen atom; 20-100wt% of the vinyl derivative represented by α, β
- A hydrolyzable resin composition characterized by copolymerizing 80 to 0 wt% of an ethylenically unsaturated monomer in an inert solvent in the presence of a radical polymerization initiator to obtain a resin composition with a molecular weight of 3,000 to 50,000. A manufacturing method is provided. Vinyl derivative of general formula (1) used as a reaction raw material in the method of the present invention Among them, those with k=0 are, for example, monochlorovinyl acetate,
Vinyl cyanoacetate, vinyl trichloroacetate, vinyl dichloroacetate, vinyl chlordifluoroacetate,
Vinyl 2-chloropropionate, vinyl o,m,p-chlorobenzoate, vinyl p-cyanobenzoate, vinyl p-nitrobenzoate, vinyl 2,4-dichlorobenzoate, 2,3,4,5-tetrachlor Most of the monomers, such as vinyl benzoate, are readily available as existing monomers. Also, for k=1, the formula (In the formula, R ₁ is hydrogen or a methyl group; l and m are each 0 or an integer of 1 to 4; R ₂ is hydrogen, a methyl group, or a hydroxyl group; X is a hydroxyl group when R ₂ is hydrogen or a methyl group; , when R ₂ is a hydroxyl group, it is hydrogen; and X can form a cyclic oxide with R ₂ ).
It can be easily synthesized by reacting a carboxylic acid represented by R ₃ COOH or its reactive derivative, and representative examples include cyanoacetic acid, chloroacetic acid, m-nitrobenzoic acid, fluoroacetic acid, etc. and glycidyl Examples include reaction products such as (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate. Further, the α,β-ethylenically unsaturated monomer copolymerized with the vinyl derivative monomer (1) mentioned above includes alkyl esters of acrylic acid and methacrylic acid, vinyl monomers such as vinyl chloride, vinyl acetate, methyl These include vinyl ether, butadiene, cyclohexene, styrene compounds, etc., and may also be unsaturated monomers having hydroxyl groups, carboxyl groups, etc. This vinyl derivative and the α,β-ethylenically unsaturated monomer are combined in a specific ratio in an inert solvent in the presence of a radical polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile to produce a polymer with a molecular weight of 3,000 to 50,000. They are copolymerized to form a polymer composition. Copolymerization of vinyl derivatives with k=0, such as monochlorovinyl acetate, and α,β-unsaturated monomers, such as vinyl acetate, has already been described in many documents and is well known. However, all conventionally known techniques utilize monochlorovinyl acetate as a raw material for crosslinkable polymers for elastomers whose main raw materials are unsaturated monomers.
13372; JP 49-36822; JP 49-38026; JP 49-92177; JP 50-96645, etc., the amount of vinyl α-halogenalkanecarboxylate used is based on the total amount of monomers. It was limited to 0.1 to 15 wt% at most, and increasing the amount beyond this was considered undesirable in view of the reaction characteristics of the copolymer.
However, in the present invention, the vinyl derivative of general formula (1) having an electron-withdrawing group, such as an acyl group carrying a halogen, is incorporated into a linear polymer chain, and the resulting copolymer is used as it is as a paint vehicle. It is hydrolyzed in slightly alkaline seawater and used for the purpose of imparting hydrophilic groups to the copolymer. If the proportion is small, it will not provide sufficient solubility to the resin and will not meet the purpose of the invention. The present inventors have discovered that the vinyl derivative I having an acyloxy or benzoyloxy moiety carrying an electron-withdrawing group contains 20 to 100 wt of the total amount of monomers.
%, more preferably 40 to 100 wt%, the resin dissolves in seawater after hydrolysis and the object of the present invention can be achieved. It can be clearly distinguished from the prior art. Furthermore, it is known that a hydrolyzable resin composition can be obtained by radical polymerizing a vinyl derivative having a benzoyloxy moiety having an electron-withdrawing group or a compound of general formula I where k=1 to an α,β-unsaturated monomer. It has not been done. In this way, in the present invention, the vinyl derivative and the α,β-ethylenically unsaturated monomer are copolymerized in a specific ratio, and the molecular weight useful as a resin vehicle is about 3,000 to 50,000, preferably 5,000 to 5,000. 20,000 polymer compositions are obtained. As already mentioned, the resin composition obtained by the method of the present invention can be used as it is as a resin vehicle for ship bottom paint, and when painted, it will not be hydrolyzed in a neutral atmosphere and will provide a stable and sufficiently strong coating film.
It is gradually hydrolyzed in seawater, separating and releasing R ₃ COOH, and the resin itself acquires hydrophilic groups and dissolves. Therefore, the α,β-ethylenically unsaturated monomer does not require a hydrophilic group such as a hydroxyl group or a carboxyl group, and it is preferable from the viewpoint of coating film stability that it does not contain a hydrophilic group. It is permissible to carry a hydrophilic group on the α,β-ethylenically unsaturated monomer to the extent that the resin itself does not dissolve or swell significantly until it is hydrolyzed in seawater. In addition, especially when the amount of vinyl derivative I is small, the α,β-ethylenically unsaturated monomer may be supported with a certain amount of hydrophilic groups, and the hydrophilic groups derived from the hydrolysis of vinyl derivative I and α, It has also been confirmed that it is preferable to render the hydrolyzed resin water-soluble through the interaction of hydrophilic groups supported on the β-unsaturated monomer. The present invention will be explained below with reference to Examples. Parts and parts by weight unless otherwise specified. Further, in this specification, the molecular weight of the resin is the number average molecular weight (measured by Gell Parmilation Chromatography). Example 1 40 parts of xylene was added to a three-necked flask equipped with a reflux, a stirrer, and a dropping funnel, kept at 80°C, and 20 parts of vinyl acetate and 80 parts of monochlorovinyl acetate were added thereto.
and 10 parts of azobisisobutyronitrile were added dropwise over 5 hours. After 2 hours of dropping, add 10 parts of methyl isobutyl ketone and 0.2 parts of azobisisobutyronitrile.
The mixture was heated to 90°C and reacted for 2 hours. Varnish A having a viscosity of Z ₁ and a solid content of 65.2% (resin molecular weight of 11,000) was obtained. Example 2 80 parts of vinyl p-chlorobenzoate, 20 parts of vinyl acetate
The viscosity Z,
A resin solution with a solid content of 64.8% (resin molecular weight 10,500) was obtained. This is called varnish B. Example 3 80 parts of vinyl p-cyanobenzoate, 20 parts of vinyl acetate
The viscosity Z ₁ ,
Resin solution with solid content 65.0% (resin molecular weight 11000)
I got it. This is called varnish C. Example 4 A resin solution with a viscosity of Y and a solid content of 64.7% (resin molecular weight
9800) was obtained. This is called varnish D. Example 5 80 parts of vinyl p-nitrobenzoate, 20 parts of vinyl acetate
The viscosity was determined in the same manner as in Example 1 except that parts were used.
Z ₁ , resin solution with solid content of 65.1% (molecular weight of resin
10000) was obtained. This is called varnish E. Example 6 The viscosity
A 64.2% resin solution (resin molecular weight 9200) was obtained.
This is called varnish F. Example 7 The same method as in Example 1 was used except that 20 parts of trichlorovinyl acetate, 40 parts of monochlorovinyl acetate, 30 parts of vinyl acetate, and 10 parts of styrene were used, and the viscosity Z ₁ and solid content were
A 64.4% resin solution (resin molecular weight 13000) was obtained.
This is called varnish G. Example 8 A resin solution with a viscosity of X and a solid content of 64.0% (resin molecular weight
8800) was obtained. This is called varnish H. The following production examples 1 to 3 are production examples of the vinyl derivative of general formula (1) used in the present invention. Production Example 1 In a three-necked flask equipped with a reflux device and a stirrer, 55 parts of glycidyl methacrylate, 45 parts of cyanoacetic acid, 0.2 parts of monoethanolamine, 0.3 parts of hydroquinone,
40 parts of dimethylformamide was added and reacted at 120° C. for 2 hours while bubbling air, then the reaction product was poured into water and neutralized with an aqueous NaHCO ₃ solution. After neutralization, the reaction product was thoroughly washed with water, the reaction product was extracted with ether, the solvent was removed from the extract, and the vinyl ester of cyanoacetic acid (general formula 1, R ₁ = CH ₃ , k = 1, l = 1, m=1, _R2
=OH, _R3 =CN- _CH2- ) 65 parts were obtained. This is called monomer A. Production Example 2 A vinyl ester of m-nitrobenzoic acid (general formula 1, R ₁ = CH ₃ , k = l =m=1, _R2 =OH,

[Formula]) 82 copies were obtained. This is called monomer B. Production Example 3 Add 60 parts of 2-hydroxyethyl methacrylate, 105 parts of fluoroacetic acid, 0.3 parts of para-toluenesulfonic acid, 1.0 parts of hydroquinone monomethyl ether, and 30 parts of toluene to a 3-necked flask equipped with a refluxer, decanter, and stirrer, and bubble air. The esterification reaction was carried out at 130°C for 5 hours while dehydrating.
Toluene was distilled off under reduced pressure. Next, in the same manner as in Production Example 1, a vinyl ester of fluoroacetic acid (general formula 1, R ₁ =CH ₃ , k = 1, l = 1, m
=0, _R2 =H, _R3 = _F.CH2- ) 35 parts were obtained.
This is called monomer C. Example 9 A resin solution with a viscosity W and a solid content of 65.2% (resin molecular weight 9000) was prepared in the same manner as in Example 1 except that 80 parts of monomer A synthesized in Production Example 1 and 20 parts of methyl methacrylate were used. Obtained. This will be used as varnish. Example 10 A resin solution with viscosity P and solid content of 64.2% (resin molecular weight
7500). This is called varnish J. Example 11 A resin solution (resin molecular weight 8600) with a viscosity of Ta. This is called varnish K. Examples 12-16 The following monomers were reacted in the same manner as in Example 1,
A varnish as shown in Table 1 was obtained.

[Table] For comparison purposes, the following comparative varnishes were made. Comparative Varnish 1 A resin solvent obtained in the same manner as in Example 1 using 13 parts of monochlorovinyl acetate and 87 parts of vinyl acetate. Comparative varnish 2 10 parts of monochlorovinyl acetate, 85 parts of vinyl acetate,
Resin solution comparison varnish 3 obtained in the same manner as in Example 1 using 5 parts of 2-hydroxyethyl methacrylate Resin solution comparison varnish obtained in the same manner as in Example 1 using 50 parts of methyl methacrylate and 50 parts of styrene 4 Comparative example of resin solvent obtained by polymerizing 100 parts of vinyl acetate according to the method of Example 1 Each of the varnishes of Examples 1 to 16 and the comparative varnish were coated on a glass plate with a length of 60 mm and a width of 50 mm so that the dry film thickness was Coat the resin to a thickness of 100μ, dry at 105°C for 3 hours, remove the solvent component, and accurately weigh to obtain the initial weight of the resin. Next, this glass plate was immersed in 350 cc of an alkaline aqueous solution with a pH of 10, held at 40°C for 18 hours, and then taken out, thoroughly washed with water, dried, and accurately weighed to obtain the final weight. The degree of hydrolysis elution of each resin was calculated using the following formula: degree of hydrolysis elution=initial weight−final weight/initial weight The results are shown in Table 2.

【table】

[Table] From the above, it is clear that the resin composition according to the present invention is hydrolyzed and eluted under weak alkalinity.

Claims (1)

[Claims] 1. General formula [In the formula, R ₁ is hydrogen or a methyl group; k is 0 or 1; l and m are each 0 or an integer of 1 to 4; R ₂ is hydrogen, a hydroxyl group, or a methyl group; R ₃ is [Formula] or [Formula] A group represented by; n is 0 or an integer of 1 to 6; X ₁ is a cyano group, a nitro group, or _a halogen atom;
X ₄ represents hydrogen, a cyano group, a nitro group, or a halogen atom respectively] and 20 to 100 wt% of the vinyl derivative represented by
- A hydrolyzable resin composition characterized by copolymerizing 80 to 0 wt% of an ethylenically unsaturated monomer in an inert solvent in the presence of a radical polymerization initiator to obtain a resin composition with a molecular weight of 3,000 to 50,000. manufacturing method.