JPH02132165A - Corrosion-resistant coating compound composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent corrosion resistance, wetting properties to metallic materials and weather resistance by blending a specific epoxy resin and silicone resin with a curing agent of epoxy resin, ketoxime silane compound and corrosion-resistant pigment in a fixed ratio. CONSTITUTION:The aimed composition containing (A) a bisphenol type epoxy resin having 160-2,000 epoxy equivalent, (B) a silicone resin shown by formula I (R is CH3 or phenyl; k and m are 0-3 and are not 0 at the same time; n is 5-500), (C) a curing agent of epoxy resin, (D) a ketoxime silane compound and (E) a corrosionresistant pigment wherein the ratio of each component satisfies relationship shown by formula II - formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel antirust coating composition. More specifically, the present invention relates to a rust-preventing paint composition that is suitable for coating iron-based materials and has excellent rust prevention properties and good wettability and weather resistance for metal materials.

[Prior Art] Conventionally, rust-preventing paints for iron-based materials include a number of resin-based paints, such as oil primers, aminoalkyd resin primers, vinyl resin primers, phenolic resin primers, chloride rubber primers, epoxy resin primers, and urethane resin primers. The following are used. Among these anti-corrosion paints, epoxy resin-based paints are characterized by the excellent properties of the epoxy resin itself, such as adhesion to metal materials, hydrolysis resistance, alkali resistance, chemical resistance, and oxidative deterioration resistance. Because of its excellent properties, it is regarded as particularly important as an anticorrosive paint and is widely used, including in the heavy-duty anticorrosion field.

This epoxy resin-based anti-rust paint usually has a bisphenol type epoxy resin as its main component, and contains lead red, zinc white, red iron oxide, chromic acid or its salts, calcium leadate, lead cyanamide, zinc powder, anoremi powder, etc. It is contained as a rust-preventive pigment and is provided in the form of one-component or two-component paints.

However, although this epoxy resin-based anti-rust paint has superior rust-preventing power compared to other resin-based paints as mentioned above, once rust begins to form microscopically under the paint film, rust In addition, corrosion progresses rapidly, and if rust has already formed on the surface at the time of painting, or if the rust is not sufficiently removed when repainting, the paint may not be applied to the clean surface. It has the disadvantage that the rust prevention ability is significantly lower than that of the conventional method.

Furthermore, the epoxy resin paint has poor weather resistance, and when used in a state where it is directly exposed to sunlight, it causes a so-called chalking phenomenon, and the resin itself is subject to photodeterioration.
It is not suitable for applications that require weather resistance, and due to the poor wettability of epoxy resin, it has poor wettability and permeability to the material, and may cause cissing when painted on surfaces with oil stains. There are problems such as insufficient penetration of paint into overlapping parts of materials, bolt tightening parts, etc., and rust is likely to occur in these parts.

[Problems to be Solved by the Invention] The present invention overcomes all of the drawbacks of conventional epoxy resin-based anticorrosion paints, has extremely excellent rust prevention properties, and has good weather resistance and excellent wettability for metal materials. The purpose of this work is to provide a rust-preventing paint composition that has the following properties.

Means for Solving the Problem 1 As a result of extensive research in order to develop an anticorrosive paint composition having such excellent characteristics, the present inventors found that an epoxy resin having a reactive functional group. It has been discovered that a composition containing a specific silicone resin, an epoxy resin curing agent, a certain type of silicone resin curing agent, and a rust preventive pigment in predetermined proportions can be adapted to the above object, and based on this knowledge, the present invention has been developed. I was able to complete it.

That is, the present invention provides (A) an epoxy equivalent of 160 to 20
00 bisphenol type epoxy resin, (B) general formula (OR). Si(R)3-, [OSi(R)z], OS
i(R)ih(Off)h...(1) (R in the formula is a methyl group or a phenyl group, k and m are each 0 or an integer of 1 to 3, but at the same time O. (n is an integer from 5 to 500), (C) an epoxy resin curing agent, (D) a ketoxime silane compound, and (E) an antirust pigment as main components, and each The ratio of components is based on weight, 0.05≦(B)/[(A)+(B)]
≦0.7... (II) 005≦(C) / [(A) +(C) ]≦0.
7... (III) 0≦(D) / [(B) 10(D) ]≦0.3(
■) 0.01≦ (E)/ [ (A)+ CB)+
(C)+(D)+(E)]≦0.9...(V) The present invention provides a rust-preventing paint composition that satisfies the following relationship.

The present invention will be explained in detail below.

In the composition of the present invention, there are no particular restrictions on the epoxy resin used as component (A). Resins are preferably used. In the present invention, as the epoxy resin, epoxy fiffi is 160
-2000 is used. If the epoxy equivalent is less than 160, the function as an epoxy resin may not be fully exhibited, and if it exceeds 2,000, the viscosity of the resin solution becomes too high, which tends to reduce painting workability.

The silicone resin as the component (B) in the composition of the present invention has the general formula (011), . Si(R)s-jOsi(R)21. O
One or more, preferably A methyl silicone resin or a phenyl-substituted methyl silicone resin having two hydroxyl groups is used.The silicone resin may have a linear skeleton structure or a branched skeleton structure. There may be, but
Those with a linear skeleton structure are preferable.

Silicone resins originally lack compatibility with epoxy resins, but the silicone resins according to the present invention have hydroxyl groups and have improved compatibility to some extent due to the effect of the alkylketoxime silane as component (D). , it is possible to form a dense crosslinked coating film with high uniformity.

If the silicone resin does not contain a hydroxyl group at the molecular end, the crosslinking between the silicone resins or with the epoxy resin will be insufficient, and sufficient coating strength will not be obtained. The hydroxyl group may have one or more in the molecule, but
Generally, one having two is preferably used.

The molecular weight of the silicone resin is expressed by the number of n in the general formula (I) and is selected within the range of 5 to 500. If n is less than 5, the wettability, permeability, and weather resistance inherent to the silicone resin will be insufficient, and the object of the present invention will not be fully achieved. There is a tendency to become unsuitable.

In the composition of the present invention, the epoxy resin curing agent used as component (C) is not particularly limited, and any one can be selected from those conventionally used as curing agents for epoxy resins. Examples of the epoxy resin curing agent include aliphatic amines, amino alcohols, aminoamides, polyamides, aromatic amines, cyclic amines, heterocyclic amines, unsaturated aliphatic amines, amino/resins, etc. One type may be used, or two or more types may be used in combination.

In the present invention, a ketoxymunlan compound is used as the component (D). This ketokin. The musilan compound acts as a crosslinking agent for silicone resin that reacts with the terminal hydroxyl group of the silicone resin of component (B), and also partially reacts with the active hydrogen of components (A) and (B). , is a component that contributes to the development of coating film strength. This component (D) is not necessarily required if the molecular weight of the silicone resin of the component (B) is sufficiently high, but it is generally desirable to use it for the above-mentioned purpose.

The ketoxime silane compound of component (D) may be, for example, represented by the general formula or (in the formula, Rl and R1 are each a saturated hydrocarbon group having 1 to 4 carbon atoms;
(which is a saturated hydrocarbon group)

These ketoxime silane compounds may be used alone or in combination of two or more, but methyl-tris(methylketoxime)silane and methyl-tris(ethylketoxime)silane are particularly preferred from the viewpoint of reactivity and economical efficiency. is suitable.

In the composition of the present invention, there are no particular restrictions on the anticorrosive pigment used as component (E), and any pigment can be selected from those conventionally used in antirust paints. Examples of the rust-preventive pigment include red lead, zinc white, red iron oxide, calcium leadate, cyanamide ship, chromic acid, zinc chromate, strontium chromate, lead chromate, basic lead sulfate, zinc phosphate, and aluminum phosphate. , zinc powder, aluminum powder, etc. In the present invention,
These anti-rust pigments may be used alone, or
Two or more types may be used in combination, and colored pigments, body N pigments, etc. can also be used in addition to these rust-preventing pigments, if desired.

Regarding the ratio of each component in the composition of the present invention, (B)
The ingredients are 5% to the total amount of ingredients (A) and (B).
It is necessary to use it in a range of 70% by weight. this(
If component B) 1 is less than 5% by weight, the effect of the present invention will not be fully exhibited, and if it exceeds 70% by weight, the moisture permeability and water permeability of the coating film will increase, and water resistance strength and adhesion will decrease. A tendency arises.

(C) It is necessary to use the component in an amount of 5 to 70% based on the total amount of component (A) and component (C). If the amount of component (C) is less than 5% by weight, there is a possibility that the epoxy resin will not be able to form a sufficiently crosslinked film11, and if it exceeds 70% by weight, the epoxy/resin ratio will be too low, resulting in the rust-preventing ability of the coating film. There is a tendency for the strength to decrease.

Component (D) must be used in an amount of 0 to 30% by weight based on the total amount of components (B) and (D). If the amount of component (D) exceeds 30% by weight, the coating film obtained tends to become brittle.

The content of (E) component is (A) component, (B) component, (C
) component, (D) component and (1) component,
It is appropriately selected within the range of 1 to 90% by weight, taking into account the specific gravity of the pigment used and the rust-preventing effect. If the amount of this component (E) is less than 1% by weight, a sufficient rust prevention effect cannot be obtained;
If it exceeds 0% by weight, the amount of pigment will be too much, making it difficult to form a dense film, and the rust-preventing ability will tend to decrease.

Since the coating composition of the present invention contains a large number of reactively active ingredients, it cannot take the form of a one-component type.
For example, a base paint is prepared from component (A) and component (E), component (E) and component (B). C) component, (
D) component; in the latter, (C) component and (D)
Advantageously, the ingredients are added and mixed homogeneously before use.

The anticorrosive coating composition of the present invention may optionally include additive components conventionally used in coating compositions, such as curing accelerators, antifoaming agents, and thickeners, to the extent that the object of the present invention is not impaired. , plasticizer, surfactant, anti-settling agent, anti-sagging agent, anti-color separation agent, pigment dispersant, leveling agent, anti-skinning agent,
Anti-scratch agent, anti-mold agent, ultraviolet absorber, antioxidant,
Antistatic agents and the like can be added.

The anticorrosive coating composition of the present invention is suitable for any coating method such as atomization coating, brush coating, or roll coating, and is used for direct coating on iron-based or galvanized materials.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

J3, the types of raw materials used are shown below.

(A) Component EBOKI 7 resin/Ebiguchi h 1 0 0 1 (Product name manufactured by Yuka/L EBOKI Co., Ltd.): Epokino equivalent (4 8 0) ・Epicoat 834 (Yuka/L Epoxy Co., Ltd.) (Product name): Epoquino equivalent (2 5 0) ・Evo-l--to YDO13 (Product name manufactured by Tobu Kasei Co., Ltd.): Eboki 7 equivalent (8 5 0) ・Evo-to YDO]. 1 (Product B manufactured by Tobu Kasei Co., Ltd.) Eboxy Bond (460) (I3) Component/Licone Resin Those shown in Table 1 were used.

(C) Component - Gnodomide G715T-70 (trade name manufactured by Toto Kasei Co., Ltd.): Polyamide amine (solid content 70 wt%) - DSX204 (trade name manufactured by Henkel): Modified polyamide amine (solid content 60 wt%) Other ingredients - Bentone 34 (trade name manufactured by Nanyonal Red Co., Ltd.) - Aerosil 200 (trade name manufactured by Nippon Aerosil Co., Ltd.) Example 1 A mixture of the raw materials shown in ■ in Example 1a of Table 2 with a portion of the solvent removed was prepared. The components shown in Example 1a (1) and the remaining solvent were added thereto and thoroughly mixed using a dissolver to prepare a lead-based rust-inhibiting paint.

To 100 parts by weight of the paint, 15.4 parts by weight of the epoxy resin curing agent (C) solution shown in Example 1b in Table 3 was added, and methyl-
1.7 parts by weight of tris(methylethylketoxime)silane and 0.9 parts by weight of γ-aminobutyltriethoxysilane as an additive were added and mixed uniformly to form the anticorrosive coating composition of the present invention shown in Table 4. Obtained.

Apply the rust-preventing paint composition thus obtained onto a rust-free mild steel plate and a lightly rusted mild steel plate with a brush so that the dry film thickness is approximately 80 μm. te2
It was coated twice and allowed to dry at room temperature for two weeks. Table 5 shows the results of exposing this coated plate to the coast for 3 years. As you can see from this table, for both bright plates and rust plates,
No rust was observed, and only slight chalking was observed, indicating excellent weather resistance.

In addition, when the above paint was applied with a brush to both bolts that were lightly stained with grease and bolts that had been degreased, it was confirmed that the coating workability of the bolts that were stained with grease was no different from that of degreased bolts. Ta. No repellency was observed during painting, and the paint easily penetrated into the deep areas with a single brush application, forming a continuous film.

Real 1jf! ．． Examples 2 and 3 In the same manner as in Example 1, a red rust-based anticorrosion paint was obtained using the raw materials and composition ratios of Example 2a in Table 2.

In Example 2, 14.8 parts by weight of the epoxy ψI hardener of Example 1b in Table 3, 1.9 parts by weight of methyl-tris (methyl ethyl ketoxime)/ran, and γ-amino were added to 100 parts by weight of the above paint. A rust-preventing paint composition was prepared by adding 0.7 parts by weight of brobiltrimethoxy/nran.

On the other hand, Example 3 was carried out in exactly the same manner as Example 2, except that 2.1 parts by weight of bis(methylethylketoxymethyl)methoxymethylsilane was used in place of methyl-tris(methylethylketoquine)silane in Example 2. A rust-preventing paint composition was produced.

- E The two types of coating compositions were respectively applied to two types of steel plates in the same manner as in Example 1 to produce exposed plates. The results of the exposure test are shown in Table 5.

Further, in the same manner as in Example 1, when two types of paint were applied to each bolt, no repelling occurred even on the oil-stained bolt 1, and the paint penetrated well into the threaded portion.

Example 4 In the same manner as in Example 1, a zinc dust-based anticorrosive paint was obtained with the composition number 48 in Table 2.

To 100 parts by weight of the above paint, 16 parts by weight of the cured product of Example 2b in Table 3 and 0.00 parts by weight of methyl-tris(methylethylketoxime). Part Smi and 0.9 parts by weight of γ-aminobrobyltriethoxysilane were added to obtain a rust preventive coating composition of the present invention.

The same exposure test as in Example 1 was conducted, and the results shown in Table 5 were obtained.

Further, the results of bolt coating also showed good workability, similar to Example 1.

Comparative Example 1 In the same manner as in Example 1, a Funatan anticorrosive paint was produced using the composition of Comparative Example 1 in Table 2.

To 100 parts by weight of the above paint, 30 parts by weight of the Evoquin resin curing agent of Example 1b in Table 3 was added to obtain a red lead-based comparative paint composition.

A coated plate was prepared in the same manner as in Example 1, and an exposure test was conducted. The results are shown in Table 5. Spot rust had occurred on the entire surface of the bright board system, and rust had progressed even more severely on the rust-prone board system, with some of the paint film peeling off due to rust.

Furthermore, the paint film was severely chocked, whitened, and the gloss decreased significantly.

Also, in the same way as in Example 1, when the bolt 1- was painted,
Bolts with grease stains caused numerous repellents immediately after painting. Also, when I applied paint to the threaded part of a bolt, the paint was not evenly distributed deep into the unfinished areas with one brush application. To completely cover the unfinished areas with paint 2
It was necessary to apply the brush more than once.

Comparative Example 2 Similarly to Comparative Example 1, a paint was produced with the composition of Comparative Example 2 in Table 2, and Example 2 in Table 3 was added to 100 parts by weight of this paint.
35 parts by weight of the epoxy resin curing agent b was added to obtain a red rust comparative paint composition.

The results of the exposure test are shown in Table 5. In addition, the same results as Comparative Example 1 were obtained in the paint test.

In addition, J- prepared in Examples 1 to 4 and Comparative Examples 1 and 2
Table 4 shows the blending amounts and component ratios of each component in the coating composition I.

(The following is a blank space) [Effects of the invention] According to the present invention, by blending the EBOKI 7 resin-based rust preventive and preservative with a silicone resin having a reactive functional group, the rust preventive power is dramatically improved. Even when painted with iron-based materials that generate M, the growth and progression of rust under the paint film is extremely slow, and it exhibits rust prevention properties that cannot be obtained with conventional paints for rusty surfaces. Moreover, the poor weather resistance of the paint film, which is a drawback of epoxy/resin-based paints, is improved, and since it is an epoxy resin-based paint, a rust-preventive paint that can also be used as a coating is obtained. In addition, even when painted on a dirty J'L/: surface, it is difficult to cause paint film defects such as repellency, and the paint penetrates well into overlapping parts of materials and deep areas, so there is no unpainted area. can be easily done.

Claims (1)

[Claims] 1 (A) a bisphenol type epoxy resin having an epoxy equivalent of 160 to 2000, (B) a compound having the general formula (OH)_mSi(R
)_3_-_m[OSi(R)_2]_nOSi(R)
_3_-_k(OH)_k (R in the formula is a methyl group or a phenyl group, k and m are each 0 or an integer from 1 to 3, but they are never 0 at the same time, and n is from 5 to 500. It is composed of a silicone resin represented by (an integer), (C) an epoxy resin curing agent, (D) a ketoxime silane compound, and (E) an antirust pigment as main components, and the proportion of each component is based on weight, and is 0. 05≦(B)/[(A)+(B)]≦0.70.0
5≦(C)/[(A)+(C)]≦0.70≦(D)/
[(B)+(D)]≦0.3 0.01≦(E)/[(A)+(B)+(C)+(D)
+(E)]≦0.9. 2. Component (B) has a general formula in which R is a methyl group,
It consists of a silicone resin in which n is an integer of 100 to 300, k and m are each 1, and component (D) is methyl-
The anticorrosive coating composition according to claim 1, which is tris(methylethylketoxime)silane.