JPS6157661A - Sealing composition for ship bottom paint - Google Patents

Abstract

PURPOSE:To provide the titled composition containing an acrylic resin having a glass transition point of lower than a specific temperature, and applicable even to the coating film of Long-Life A/F (popular name) or self-polishing A/F without causing the troubles such as drying, cracking, etc. CONSTITUTION:The objective composition can be produced by compounding (A) 10-70(wt)% acrylic resin having a glass transition point of <=10 deg.C with (B) preferably 90-30% one or more components such as chlorinated rubber, cyclized rubber, chlorinated polyolefin, copolymer of vinyl chloride and other vinyl-containing monomer, petroleum resin, coumarone resin, coal tar, plasticizer, etc. The acrylic resin is preferably composed of one or more monomers of formula (R1 is H or methyl; R2 is H, 1-20C alkyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl, organic tin or organic lead) and optionally a vinyl-containing monomer copolymerizable therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a sealing composition for ship bottom paint.

<Conventional technology> Conventionally, paints with an oil-based or alkyd resin vehicle have been used as the No. 1 paint on the bottom of ships, and as an alternative, solvent evaporation drying with a vehicle of chlorinated rubber or modified vinyl Type 1 has also been widely used in recent years.

And then, paint on top of these bottom No. 1 paints for the ship bottom 2 homecoming! ′
3 [was generally painted with a vehicle using the same type of resin as the No. 1 paint on the bottom of the ship.

On the other hand, as a result of the movement to pursue economic efficiency, the use of cross-linked resin paints such as epoxy resins, coal tar epoxy resins, or coal tar epoxy resins, which have anti-corrosion properties over a long period of time, has been adopted for the bottom 1 return charge. Paints that use modified vinyl resin as a vehicle have begun to be used.

Regarding ship bottom No. 2 paint, paints using oil-based or alkyd resin, chlorinated rubber, or modified vinyl resin as a vehicle contain rosin to elute the antifouling agent contained in it, and as a result of its hydrolysis and water solubilization. It will be done. It utilized the elution of antifouling agents from the paint film.

However, these paints have the disadvantage that an insoluble layer (generally referred to as a skeleton layer) is gradually formed on the surface during navigation, increasing the roughness of the bottom surface and significantly reducing the antifouling ability.

Various studies have been carried out to improve these shortcomings, and a greatly improved ship bottom 2@ paint has now been put into practical use.

Most of these are copolymers of monomers containing vinyl groups, and are mainly composed of resins generally referred to as acrylic resins.

Namely, acrylic acid or methacrylic acid or various alkyl esters thereof, hydroxyalkylnisder,
Amides, styrene, vinyltoluene, itaconic acid,
The main component is a copolymer of one type or 2FIi or more such as maleic acid, and sometimes contains a portion of a modified vinyl resin or other resin that is compatible with these copolymers, but such acrylic components Long-life Δ/ It is popularly known as F.

In addition, Nisdel copolymers of one or more of various acrylic acids or methacrylic esters, methacrylic acid or acrylic acid, and tin or organic lead, so-called organometallic copolymers, can be used to add water to coating films made of them. It has an antifouling effect due to the bound paid metal compound liberated from the polymer through zero decomposition, and the polymer itself, from which the organometallic compound has been dissociated, is gradually washed away from the surface by seawater currents, which prevents or removes the adhesion of living organisms. Therefore, organometallic copolymers have been put to practical use either alone or with the addition of various conventional antifouling agents, and are generally referred to as self-polishing A/Fs.

Under these circumstances, the No. 1 ship bottom paint and the No. 2 ship bottom paint sought to achieve the desired performance of each, and as a result, the resins used as vehicles were completely different, and therefore different types of resin paints were used. I often have to repaint.

That is, coat No. 1 paint on the bottom of the ship using coal tar, modified vinyl resin, epoxy resin, epoxy resin and coal tar, or epoxy urethane resin and coal tar as a vehicle, and directly apply the above-mentioned long-life A/F or self-polishing onto 1ζ. Painting type A/F, or in some cases using epoxy resin, epoxy resin and coal tar, or epoxy/urethane resin and coal tar as a vehicle bottom 1
After applying a binder or sealer coat on top of the No. 1 paint, a chlorinated rubber-based resin, modified vinyl resin, or modified vinyl chloride and coal tar vehicle is applied as a binder or sealer coat. F is painted.

Even if such different resin-based paints are applied over and over again, as long as the No. 2 bottom paint is applied on top of the No. 1 bottom paint, as described here, there will be no problems with drying or adhesion of the paint film. do not have.

<Problems to be Solved by the Invention> However, the outer plate of a ship's hull is damaged due to collisions with anchors or anchor chains, fenders on quay walls, and floating objects at sea, and it is difficult to repair such damaged parts with real methods. Therefore, a touch-up coat of No. 1 bottom paint is applied, but in this case, there will be areas around the damaged area where the No. 1 bottom paint will be coated over the No. 2 bottom paint.

Also, depending on the type of bottom No. 2 paint, it may be desirable to coat the entire surface of the old bottom No. 2 paint film remaining on the bottom surface with a brimer as a binder, and then apply the bottom No. 2 paint.

In such cases, if you apply a conventionally known ship bottom No. 1 paint or primer on a long-life A/F or a self-polishing A/F made of a vehicle based on so-called acrylic resin, only the surface will dry. However, the lower layer of long life A/F or self-polishing type Δ/F absorbs solvent and softens, and normally each paint alone dries and solidifies within a few hours, but in this case, the lower layer dries and solidifies. is extremely U
This causes problems such as drying that takes 2 to 3 days or cracks in the primer film on the surface.

Also, if the No. 1 paint on the bottom of the ship is tar epoxy paint,
Even though the cross-linking reaction of this coating film has finished and the film itself has hardened, the old A/F film beneath it remains softened due to the presence of solvent, and the coating film remains intact during the voyage after the ship is docked. often causes peeling.

Means for Solving the Problems> The present inventors have conducted extensive research to solve the above-mentioned drawbacks of ship bottom paints, and as a result they have arrived at the present invention.

That is, the present invention uses an acrylic resin having a glass transition point of 10° C. or lower as a sealing composition for coating on a long-life A/F or self-polishing coating film made of a vehicle mainly composed of so-called acrylic resin. A conventionally known ship bottom 1 is a composition containing 10 to 70% by weight of a system resin.
It has been discovered that the drawbacks of paints or primers can be overcome and that it can be painted over the old paint film of long-life A/Fs or self-polishing A/Fs without any problems.

Effect> The reason why the sealing composition of the present invention does not cause problems even when applied on the old A/F paint film is not clear at all, but Δ
Contains an acrylic resin similar to that of the /F coating film, and furthermore, the resin has a glass transition point of 10°C as described in this invention.
In the following cases, even if the solvent in the composition temporarily penetrates into the underlying old A/F membrane layer, the distribution of the solvent between the old A/F membrane and the composition of the present invention is not balanced. It is thought that this causes the solvent to volatilize between the old A/F film and the composition film in the lower layer, that is, there is no difference in drying, and as a result, the overall drying and solidification of the paint film is normal. It will be done.

In this way, if the sealing composition of the present invention is applied onto the old A/F membrane and is dried and solidified normally, it will not dry even if a new AlFt material or tar epoxy paint is applied on top of it. No obstruction or poor adhesion will occur.

゛It is essential that the acrylic resin used in this invention has a glass transition point of 10°C or lower.If the acrylic resin has a glass transition point higher than this, the effect obtained by this invention will be small, and even if the acrylic resin A primer using a resin alone as a vehicle not only does not exhibit sufficient effects, but also may exhibit unfavorable results in terms of other properties as a primer.

If an acrylic resin with a glass transition point of 10°C or less, which is the gist of this invention, is used, at most 70% of this resin can be contained in the vehicle.
It exhibits an effect even if it is contained within D% by weight, and it is possible to formulate the composition appropriately.

Further, even if an acrylic resin having the lowest glass transition point among currently known acrylic resins is used, practical effects will not be obtained unless the vehicle contains at least 10% of this acrylic resin.

The lower the glass transition point of the acrylic resin, the smaller the proportion of the acrylic resin in the vehicle may be.

Acrylic having a glass transition point of 10°C or less used in this invention,
The acrylic spinning wheel matrix for obtaining acrylic acid or methacrylic acid is methyl ester, ethyl ester, propyl ester, butyl ester, hexyl ester, [-butyl ester, 2-ethylhexyl ester, ocdyle ester, lauryl ester] , alkyl esters such as stearyl ester, hydroxyalkyl esters such as hydroxyethyl ester and hydroxypropyl ester, aminoalkyl esters such as dimethylaminoethyl and dimethylaminoethyl, flukoxyalkyl esters such as methoxyethyl ester and ethoxyethyl ester, acrylamide, Examples include methacrylamide, acrylonitrile, methacrylonitrile, cyclohexyl ester, benzyl chloride, organic tin esters such as tributyltin and triphenyltin, and lead esters such as 1-liptyl lead and triphenyl lead.

Examples of vinyl-containing monomers that can be copolymerized with these include styrene, vinylstyrene, vinyltoluene, oleic acid, fumaric acid, itaconic acid, vinyl acetate, and vinyl chloride. The effects of the present invention can be exhibited by polymerizing or copolymerizing two or more of these monomers in an appropriate ratio to obtain a polymer having a glass transition point of 10'C or less. .

As described above, the main factor in the composition of the present invention is the glass transition point temperature, and if the molecular weight of the polymer or copolymer is too high, it is unfavorable from the viewpoint of coating workability, and the appropriate molecular weight is 200,000 or less.

The composition of this invention is then used as a vehicle with a glass transition temperature of 1
9 for acrylic resin 10 = 70% by weight below 0°C
Resins that can be used as a component of 0 to 30% of heavy nails include:
It may be a paint that has traditionally been used as a solvent evaporation type ship bottom No. 1 paint or a vehicle for brimer, such as chlorinated rubber, cyclized rubber, chlorinated polyethylene, chlorinated polyolefin such as chlorinated polypropylene, and vinyl chloride. and vinyl chloride and one or more vinyl group-containing single substances such as vinyl acetate, vinyl chloride and vinyl isomethyl ether, vinyl chloride and vinyl isobutyl ether, vinyl chloride, vinyl acetate, and maleic acid, so-called modified vinyl chloride. resin, petroleum resin, coumaron resin, coal tar,
Coal tar pitch and, if necessary, various plasticizers may be used alone or in combination of two or more depending on the required properties of the composition.

In order to obtain the composition of the present invention, extender pigments such as calcium carbonate, talc, and pallite, antirust pigments such as zinc phosphate, aluminum phosphate, zinc chromate, and red lead, aluminum powder, coloring pigments, stabilizers, pigment wetting agents, dispersants,
It is effective to appropriately use materials commonly used in paints, such as leveling agents and anti-flow agents.

<Example> Hereinafter, this invention will be explained in detail with reference to Examples.

Note that all parts are parts by weight.

Example 1 250 parts of butyl acrylate and 150 parts of xylene were charged into a flask equipped with a reflux cold W pipe, a stirrer, and a thermometer, the temperature was raised to 90-100°C, 2 parts of benzoyl peroxide was added, and the temperature was After holding for 4 hours, 1 part of benzoyl peroxide was further added, and 1 part of benzoyl peroxide was added twice every 2 hours to complete the reaction.

The contents were then cooled and 100 parts of xylene was added to
% solution. The glass transition point of this solution was -45°C.

Example 2 150 parts of xylene was charged into a flask equipped with a reflux condenser, a stirrer, a hygrometer, a dropping funnel, etc., and the temperature was adjusted to 90-10
Maintained at 0°C, 175 parts of butyl acrylate, 50 parts of butyl methacrylate, 25 parts of styrene, 1 part of benzoyl peroxide.
Mix and dissolve 1 part and dropwise over 2 hours, then 2
1 part of benzoyl peroxide was added three times each time to complete the polymerization reaction. Cool the contents in IJI L, xylene 1.
00 parts were added to give a 50% concentration polymer. The glass transition point of this polymer was -20°C.

Example 3 150 parts of xylene was charged into a flask equipped with the same equipment used in Example 2, and kept at 90 to 100°C, and 190 parts of egur acrylate, 50 parts of ethyl methacrylate, and 10 parts of 2-hydroxylethyl methacrylate were added. A mixed solution of 2 parts of benzoyl peroxide was added dropwise over a period of 2 hours, and then 1 part of benzoyl peroxide was added three times every 2 hours to complete the polymerization.

Next, cool the contents and add 100 parts of xylene to make 50%
It was made into a polymer with a certain concentration. The glass transition point of this polymer is 12
It was ℃.

Example 4 Polymers with 50% WA degree obtained in Examples 1 to 3 above and commercially available resin solution Pyomet 300 (M&T
Biomet 303J (manufactured by M&T Co., Ltd., 50% solution of methyl methacrylate-tributyltin methacrylate copolymer, glass transition point 0'C) 5
Sealing compositions for ship bottom paints having the formulations of Formulation Examples 1 to 7 shown in Table 1 were prepared using a 0% solution (glass transition point: 8°C).

Next, an iron plate that has been previously coated with an anti-corrosion coating is prepared, and an antifouling paint made of a vehicle mainly composed of acrylic resin is applied to this iron plate, and a dry film of the sealing composition having the formulations 1 to 7 described above is applied to the iron plate. Paint to a thickness of approximately 5Q <μ, and allow these paint films to dry.

and examined the surface condition.
6 The results are shown in Table 2, demonstrating that the sealing composition of the present invention is superior to the conventional brimer shown in Comparative Example.

Furthermore, even when the No. 2 ship bottom paint was further applied after drying these sealing compositions, the underlying No. 2 ship bottom paint film did not soften (it was good).

In addition, when a coal tar epoxy paint was further applied on top of these sealing compositions, the results were good with less softening compared to the comparative examples.

(Note) +11: 50% resin solution is obtained in Examples 1-3.

(2J: 40% chlorinated rubber solution is a solution of 40a hanging part of chlorinated rubber (trade name: Alloprene CR10) manufactured by ICI Ltd., UK) in 1 part of xylene 60fla.

(31: What is a 2% modified vinyl resin solution? 25 parts of vinyl chloride resin (trade name: Vinyrite Resin VAGH) manufactured by Union Carbide Co., Ltd. is mixed with a mixed solvent of 37.5 parts by weight of MIB K and 37.5 parts by weight of xylene. It is dissolved in

+4): What is the 40% modified vinyl resin solution? Vinyl chloride resin (trade name: Laroflex M
P45) 4011 parts dissolved in 60 i fi parts of xylene.

[5): 50% petroleum resin solution is petroleum resin manufactured by Mitsui Ishiura Chemical Co., Ltd. (trade name Vetrogin 120) 50fNf1
1 part is dissolved in 50 parts of xylene.

(6): As the plasticizer, Seleclor 48 manufactured by ICI, UK was used.

Table 2 shows 1 0"[" 1 Big mouth IC+ Eye "1 Eye" -1 rl To8--4 Shi-1 Giant-11 Giant 1 Country-1 [(1) 1 Big mouth 7 Ni (note) (1 ) Paint-resistant i2 painted on steel plate - A; Paint is made by Kobe Paint Co., Ltd. (product name: KP Coat A/F H, T, S-T) Paint is mainly composed of acrylic resin. Paint B is nitributyltin methacrylate copolymer. Manufactured by Kobe Paint Co., Ltd. (product name: KP Ace SP A
/F 100) Paint C: Manufactured by Chugoku Paint Co., Ltd. (trade name: AF SEA CLO Z-1OO) containing a tributyltin methacrylate copolymer as the main component Paint D: 1~Japanese paint containing a tributyltin methacrylate copolymer as the main component It is a paint made by Yushisha (trade name: 3L No. 2).

(2) The evaluation criteria for the dry state is: O: Good - No marks left when the paint surface is pressed △: Fairly good - No marks left when the paint surface is pressed ×: Poor - No marks left when the paint surface is pressed It cannot be shifted.

It was a hailstorm.

Effects〉 Table 1) S Excellent results were shown in both film and dry conditions.

Patent Applicant Kobe Paint Co., Ltd. Representative Patent Attorney Kazu 1) Town Procedures Negotiations (spontaneous) October 12, 1980 Patent Application No. 179919 2, Name of Invention Sealing Composition for Ship Bottom Paint 3. Relationship between the person making the amendment and the case Patent applicant address: 4th floor, Shinko Pill, 8 Kaigandori, Chuo-ku, Kobe Name: Kobe Paint Co., Ltd. 4 Agent address: 1-18-18 Nakatsu, Oyodo-ku, Osaka Ming M
Contents of amendments in the "Scope of Claims" and "Detailed Description of the Invention" columns of Book U: 1. Patent -1 The scope of the claim will be corrected as shown in the attached sheet.

2 Line 5 of member 17 of the specification: ``(Product name Alloprene CR-10) J is corrected to [(Product name Alloprene R-10) J.

3. In the item of Table 2 on page 18 of the same, "after coating with brimer" is corrected to "after coating with the sealing composition of the present invention or brimer".

4. In the item of Table 2 on page 18 of the same, "Brymer drying" is replaced with "Sealing composition of the present invention or Brimer drying"
I will correct it.

5 Page 19, line 9 Correct J to say "Zi-kuro" as "Shi-flo".

Claims (1) A sealing composition for ship bottom paint, characterized in that the component contains 10 to 70% by weight of an acrylic resin having a glass transition point of 10° C. or lower.

(2) Acrylic resin with a glass transition point of 10°C has the general formula &.

CH2-C-Co OR2 (However, R1 is hydrogen or a methyl group, R1 is hydrogen or a furkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group,
consisting of one or more monomers represented by (aminoalkyl group, alkoxyalkyl group, organotin group, or organic lead group) or a vinyl group-containing monomer copolymerizable with these monomers. A sealing composition for ship bottom paint according to claim 1, characterized in that:

(3) 90 to 30% by weight of components other than the acrylic resin in the composition are chlorinated rubber, cyclized rubber, chlorinated polyolefin, a copolymer of vinyl chloride and a vinyl group-containing 1fIu body, petroleum resin, The sealing composition for ship bottom coating according to claim 1, characterized in that it contains one or more of coumaron resin, coal tar, plasticizer, etc.

[1

Claims (3)

[Claims] (1) A sealing composition for ship bottom paint, characterized in that the component contains 10 to 70% by weight of an acrylic resin having a glass transition point of 10° C. or lower. (2) Acrylic resin with a glass transition point of 10℃ has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 is hydrogen or a methyl group, R_2 is hydrogen or an alkyl group with 1 to 20 carbon atoms, hydroxy or a vinyl group-containing monomer copolymerizable with these monomers. The sealing composition for ship bottom paint according to claim 1, characterized in that it consists of the following ingredients: (3) 90 to 30% by weight of components other than the acrylic resin in the composition are chlorinated rubber, cyclized rubber, chlorinated polyolefin, copolymers of vinyl chloride and other vinyl group-containing monomers,
2. The sealing composition for ship bottom paint according to claim 1, which contains one or more of petroleum resins, coumaron resins, coal tar, plasticizers, and the like.