JP3210815B2 - Room temperature curable organopolysiloxane composition and cured product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a cold-curable organopolysiloxane composition and an antifouling paint comprising the composition. More specifically, since the present invention does not contain a toxic antifouling agent, it is free from environmental pollution and is safe in environmental hygiene, and a room temperature-curable organopolysiloxane composition capable of maintaining the antifouling effect for a long period of time. And an antifouling paint comprising the composition.

[0002]

2. Description of the Related Art Since seawater introduction pipes, marine structures, ship bottoms, and the like have been in contact with seawater for a long period of time, marine organisms may adhere to the surface and cause various adverse effects. Conventionally, to prevent this, paint containing cuprous oxide, tributyl tin, triphenyl tin, etc. is applied to the surface such as the bottom of the ship,
Prevents the attachment of marine organisms. However, in recent years, there has been a problem that these drugs elute into the sea and contaminate fish and shellfish.

[0003] Therefore, methods for preventing the attachment of marine organisms without using these agents have been studied in recent years.
It is known that a paint containing silicone rubber as a vehicle is particularly effective. For example, an antifouling paint containing an organic compound such as liquid paraffin in a silicone rubber vehicle (see JP-A-53-79980), and a low surface tension compound of a petroleum fraction such as petrolatum in a silicone rubber vehicle. Antifouling paint (JP-A-60-3433)
Japanese Patent Application Laid-Open No. 54-26826, Japanese Patent Publication No. 57-16868, and the like. Further, recently, instead of these organic substances, antifouling paints containing various modified silicone oils having no compatibility with the silicone vehicle have been proposed and actually put to practical use.

Further, JP-A-3-255169 describes an antifouling paint comprising a reaction-curable silicone resin composition and a silicone resin having an alkoxy group at a molecular terminal.

[0005]

However, although the above antifouling paint has antifouling properties for a period of about 1 to 2 years, it cannot be expected to have antifouling properties for a longer time. Therefore, if an antifouling paint capable of achieving antifouling properties over a long period of time is obtained, its industrial value is extremely large.

[0006]

As a result of diligent efforts to solve the above-mentioned problems, a cured product obtained from the below-mentioned curable organopolysiloxane composition has excellent antifouling properties over a long period of time. To complete the present invention.

That is, the present invention relates to (A) 100 parts by weight of an organopolysiloxane whose both terminals are blocked with a silanol group or a hydrolyzable group, and (B) a compound represented by the general formula (1) R ¹ _a SiX _{4 -a} (where R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms;
Is a hydrolyzable group, and a is 0 or 1).
In an amount of 0 parts by weight, (C) general formula (2)

[0008]

Embedded image

[0009] The organopolysiloxane represented by
In R¹Is the same as the component (B), and Z is an oxygen atom
Represents a polyether group bonded to Si. Also Y
Is R ¹Or Z is the same as R¹, Z are of the same kind
Or different types. m is 0-2
000, and n is 1 to 1000. ) From 1 to 20
Characterized by being contained in an amount of 0 parts by weight, at room temperature
It is a curable organopolysiloxane composition.

In the present invention, the component (A) and the component (B)
When the organopolysiloxane as the above-mentioned component (C) is added to the room-temperature-curable organopolysiloxane composition comprising the above components, when the component (C) is immersed in the sea for a long time, the -SiOC bonding portion Is hydrolyzed, and the polyether groups are bleeded to the surface of the organosiloxane. This prevents marine organisms from adhering, so that the paint exhibits an effective antifouling property for a long period of time.

[0011] The cold-curable organopolysiloxane composition of the present invention has an advantage in that, at an early stage, compared to the conventional paint, the polyether group is bonded to the siloxane, so that liquid paraffin and other organic compounds can be used. Unlike the compounds, they are compatible with each other without bleeding in large quantities at once, and after a certain period of time, elution is continued because the hydrolyzed polyether groups are incompatible with the silicone vehicle.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The cold-curable organopolysiloxane composition according to the present invention and a coating material containing the same will be specifically described below.

The organopolysiloxane which is the component (A) constituting the cold-curable organopolysiloxane composition of the present invention has its molecular chain terminal blocked by a silanol group or a hydrolyzable group.

An organopolysiloxane in which both ends of such a molecule are blocked with a silanol group or a hydrolyzable group can be represented by the following general formula (3).

[0015]

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Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X is a hydrolyzable group or a hydroxyl group,
a is an integer from 0 to 3. n is 10 to 2000. ).

R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group, or a cycloalkyl group such as a cyclohexyl group. Group,
Aralkyl groups such as benzyl group and 2-phenylethyl group, or chloromethyl groups in which part or all of the hydrogen atoms bonded to carbon atoms of these groups have been substituted with halogen atoms, cyano groups, etc., 3,3,3-trifluoro Examples thereof include a propyl group and a 2-cyanoethyl group. Among these, carbon numbers 1 to 1
0, preferably 1-8 unsubstituted or substituted monovalent hydrocarbon groups are preferred. N is an integer of 5 or more, and the viscosity of the organopolysiloxane (A) is 25 to 500,000.
cs, preferably 1000 to 100000 cs.

X is a hydroxyl group or a hydrolyzable group,
Examples of hydrolysable groups include methoxy, ethoxy,
Propoxy group, butoxy group, methoxyethoxy group, alkoxy group such as ethoxyethoxy group, acetoxy group, propionoxy group, butyroxy group, acyloxy group such as benzoyloxy group, isopropenyloxy group, isobutenyloxy group, 1-ethyl-2 -Alkenyloxy groups such as methylvinyloxy group, dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group, iminoxime groups such as cyclopentanoxime group, cyclohexanoxime group, N-methylamino group, N-ethylamino Group,
N-propylamino group, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, amino group such as cyclohexylamino group, N-methylacetamido group, amide group such as N-methylbenzamide group, Examples include aminooxy groups such as N, N-dimethylaminooxy group and N, N-diethylaminooxy group.

The organosilane or its partial hydrolyzate as the component (B) constituting the composition of the present invention is R ¹ _a SiX _4-a (where R ¹ is a non-C 1-8 non-C ¹ A substituted or substituted monovalent hydrocarbon group, X is a hydrolyzable group, and a is 0 or 1), or an organosilane or a partially hydrolyzed product thereof; And acts as a crosslinking agent for the organopolysiloxane.

R ¹ and X are the same as described above. Examples of the organosilane (B) represented by R ¹ _a SiX _4-a include methyltrimethoxysilane, methyltri (methylethylketoxime) silane, methyltripropenyloxysilane, methyltriacetoxysilane, and methyl of these silane compounds. Examples thereof include silanes in which the group is substituted with a vinyl group, a phenyl group, a trifluoropropyl group, and the like, and further, a partial hydrolyzate thereof.

The content of the organosilane (B) is determined by the amount of the organopolysiloxane 10 as the component (A).
1 to 30 parts by weight, preferably 2 to 20 parts by weight with respect to 0 parts by weight. If the amount is less than 1 part by weight, the crosslinking is insufficient because the amount is too small, while if it is more than 30 parts, the cured product becomes hard, The properties as a paint may be impaired or the cost may increase.

Next, the organopolysiloxane as the component (C) used in the cold-curable organopolysiloxane composition of the present invention has the general formula (2)

[0023]

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An organopolysiloxane represented by the formula: In the formula, R ¹ is the same as the component (B) and has 1 to 1 carbon atoms.
A monovalent hydrocarbon group having 8 unsubstituted or substituted groups, and Z represents a polyether group bonded to Si via an oxygen atom. m is 0 to 2000, and n is 1 to 10
00. The carbon number of the polyether group is desirably in the range of 3 to 200, preferably in the range of 4 to 100.

Examples of the polyether group include a polyoxyethylene group and a polyoxypropylene group.
Further, it may be a polyoxyethylene-polyoxypropylene group. In the formula, Y is the same as R ¹ or Z, and R ¹ and Z may be the same or different. Further, the polyether group preferably has a double bond at a terminal.

Such a component (C) is composed of the component (A) 10
1 to 200 parts by weight, preferably 5-1 to 0 parts by weight
It is desirably 00 parts by weight. If the amount is less than 1 part by weight, the effect of maintaining the antifouling property is reduced, while if it exceeds 200 parts by weight, the strength of the coating film is reduced, resulting in poor durability when immersed in the sea. I will.

Such an organopolysiloxane (C)
Examples of the compound include the following compounds. Me ₃ SiO (SiMe ₂ O) ₃₀ (SiMe (OEO ₈ CH ₂ CH = CH ₂ ) O) ₅ SiMe ₃ Me ₃ SiO (SiMe ₂ O) ₃₀ (SiMe (OEO ₁₂ PO ₁₂ CH ₂ CH = CH ₂ ) O ) ₅ SiMe ₃ Me ₃ SiO (SiMe ₂ O) ₂₀ (SiMePhO) ₁₀ (SiMe (OEO ₈ CH ₂ CH = CH ₂ ) O) ₅ SiMe ₃ Me ₃ SiO (SiMe ₂ O) ₃₀ (SiMe (OEO ₈ CH ₂₎ CH = CH ₂ ) O) ₅ (SiMe (OEO ₁₂ PO ₁₂ CH ₂ CH = CH ₂ ) O) ₅ SiMe ₃ Me ₃ SiO (SiMe ₂ O) ₃₀ (SiMe (OEO ₈ CH ₂ CH = CH ₂ ) O) ₅ SiMe ₂ OEO ₈ CH ₂ CH = CH ₂ where EO represents ethylene oxide and PO represents propylene oxide.

The room-temperature-curable organopolysiloxane composition of the present invention and the antifouling paint containing this composition may optionally contain a filler for the purpose of reinforcing or increasing the amount thereof. As the filler, known fine powder silica, fumed silica, precipitated silica, diatomaceous earth, iron oxide, zinc oxide, metal oxides such as titanium oxide,
Alternatively, those obtained by hydrophobizing these surfaces with silane or the like, metal carbonates such as calcium carbonate, magnesium carbonate and zinc carbonate, asbestos, glass fibers, carbon black and the like are exemplified. If necessary, a thixotropic agent such as polyethylene glycol and a derivative thereof, a pigment, a dye, an antioxidant, an antioxidant, an antistatic agent, and a flame retardant may be added. Further, various conventionally known additives such as an organosilicon compound having a reactive organic group such as an amino group, an epoxy group, and a mercapto group as a bonding agent may be mixed.

Since such a room temperature-curable organopolysiloxane composition according to the present invention is room temperature-curable and has a property of preventing marine biofouling, a seawater introduction pipe,
It is useful as an antifouling paint for marine structures and ships. Such an antifouling paint may further contain a hydrocarbon-based solvent such as toluene, xylene, petroleum ether, a ketone or an ester for convenience of use when applied to various substrates. The antifouling paint may contain a plasticizer, an anti-sagging agent, a known antifouling agent such as silicone oil, vaseline, paraffin, liquid paraffin, wax and the like, as well as a bactericide, a fungicide and the like.

When the antifouling paint is applied,
It cures at room temperature to form a silicone rubber coating on the surface of the substrate, and this coating has the effect of exhibiting anti-biological adhesion to the sea.

[0031]

EXAMPLE 1 Dimethylpolysiloxane 1 having a viscosity of 20100 cs and having both ends of the molecular chain blocked by silanol groups
000 g and 200 g of fumed silica having a specific surface area of 200 m ³ / g were uniformly mixed with a stirrer to prepare a base compound. Then, 15 g of methyltri (methylketoxime) silane as a crosslinking agent, 0.1 g of dibutyltin dimethoxide as a catalyst, and M as an antifouling agent were used.
e ₃ SiO (SiMe ₂ O) ₃₀ (SiMe (OEO ₈ CH ₂ CH = CH ₂ ) O) ₅ SiMe ₃
Was added and uniformly stirred and mixed to prepare antifouling paint 1.

[0032]

Example 2 In Example 1, the antifouling agent was Me ₃ SiO
(SiMe ₂ O) ₃₀ (SiMe (OEO ₁₂ PO ₁₂ CH ₂ CH = CH ₂ ) O) ₅ SiMe ₃
To prepare antifouling paint 2.

[0033]

Example 3 In Example 1, the antifouling agent was Me ₃ SiO
(SiMe ₂ O) ₂₀ (SiMePhO) ₁₀ (SiMe (OEO ₈ CH ₂ CH = CH ₂ )
O) ₅ is changed to SiMe ₃ was prepared an antifouling paint 3.

[0034]

Example 4 In Example 1, the antifouling agent was Me ₃ SiO
(SiMe ₂ O) ₃₀ (SiMe (OEO ₈ CH ₂ CH = CH ₂ ) O) ₅ (SiMe (OEO ₁₂ PO ₁₂ CH
₂ CH = CH ₂ ) O) ₅ SiMe ₃ was used to prepare antifouling paint 4.

[0035]

Example 5 In Example 1, the antifouling agent was Me ₃ SiO
(SiMe ₂ O) ₃₀ (SiMe (OEO ₈ CH ₂ CH = CH ₂ ) O) ₅ SiMe ₂ OEO ₈ C
Antifouling paint 5 was prepared by changing H ₂ CH = CH ₂ .

[0036]

Comparative Example 1 An antifouling paint 6 was prepared in the same manner as in Example 1 except that no antifouling agent was added.

[0037]

Comparative Example 2 An antifouling paint 7 was prepared in the same manner as in Example 1 except that petrolatum, a substance known as an antifouling agent, was added. [Test method] The antifouling paint obtained as described above was heated at 20 ° C.
Formed into a 2 mm thick sheet in a 55% RH constant temperature room,
It was cured for days to obtain a cured product. This cured product was immersed in the sea for 24 months, and the adhesion of marine organisms to the surface was confirmed.

The results are shown in Table 1.

[0039]

[Table 1]

────────────────────────────────────────────────── ─── Continued on the front page (56) References JP-A-56-76452 (JP, A) JP-A-56-76453 (JP, A) JP-A-4-106156 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 83/06 C08K 5/54 C08L 83/12

Claims (4)

(57) [Claims] 1. An organopolysiloxane 100 wherein both ends of the molecule are blocked with a silanol group or a hydrolyzable group.
(B) R ¹ _a SiX _4-a (where R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms;
Is a hydrolyzable group, and a is 0 or 1).
(C) General formula (2) in an amount of 0 parts by weight Wherein R ¹ is the same as the component (B), and Z is Si through an oxygen atom.
Indicates a polyether group attached to an atom. Y is
It is the same as R ¹ or Z, and R ¹ and Z may be the same or different. m is 0 to 200
0 and n is 1 to 1000. ) In an amount of from 1 to 200 parts by weight of a cold-curable organopolysiloxane composition. 2. An antifouling paint comprising the cold-curable organopolysiloxane composition according to claim 1. 3. The cold-curable organo according to claim 1.
Antifouling coating containing polysiloxane composition for prevention of marine organism adhesion
Fees. 4. A formed by curing a composition or paints according to any one of claims 1 to 3 cured film.