JPH03281335A - Polyphenylene sulfide resin coated metal body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a metal body coated with polyphenylene sulfide resin.

(Prior art) Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has excellent heat resistance, hot water resistance, chemical resistance, mechanical strength, etc., and has good fluidity during melt molding, making it suitable for forming into metal objects. It is used as a coating resin.

20 When coating the metal surface with PPS resin, in order to obtain excellent coating performance, the minimum
It is necessary to bake at a high temperature of about 0.000°C to allow the hardening reaction to proceed sufficiently. Furthermore, in order to strengthen the adhesion between the resin coating layer and the metal surface, it is necessary to use a primer with excellent heat resistance.

As a primer for this type of PPS resin, for example, JP-A-58-50147 discloses a primer composition consisting of aluminum powder, zinc powder, and an initial condensate of an alkyl silicate whose alkyl group has 1 to 4 carbon atoms. has been disclosed.

(Problems to be Solved by the Invention) A PPS resin-coated metal body using the above-mentioned brimer composition has excellent adhesion between the metal body surface and the primer layer.

However, the primer layer and the PPS resin coating layer are in close contact with each other simply due to the anchoring effect of the unevenness of the interface, so the adhesion is not sufficient, and the adhesion deteriorates especially when used for a long time under hot water. Blisters on the coating
or peeling may occur.

The present invention is intended to solve these problems, and its purpose is to provide a PPS resin-coated metal body that has excellent heat resistance and excellent adhesion between both the PPS resin coating layer and the metal body. The purpose is to capture and provide.

(Means for Solving the Problems) The PPS resin-coated metal body of the present invention has a first primer layer made of a brimer composition made of a metal alkoxide or an initial condensate thereof formed on the surface of the metal body, and an organic metal system coupling agent or this coupling agent and PP
The present invention is characterized in that a second primer layer is formed using a brimer composition consisting of S resin powder, and a PPS resin is coated thereon, thereby achieving the above object.

In the present invention, in the brimer composition comprising a metal alkoxide or an initial condensate thereof used to form the first primer layer, the metal alkoxide is generally
(01?') (OR") (OR'). Here, the gate represents a metal, Ti, Zr5A1., G
A metal selected from a, In, Si, Ge, Sn, and Nb is preferable, and R1, R2, R3, and R4 represent the same or different alkyl groups, and an alkyl group having 1 to 18 carbon atoms is preferable. If the number of carbon atoms in the alkyl group exceeds 18, it will be easily decomposed by heat. Note that the metal alkoxide also includes a metal matrix.

Specific examples of such metal alkoxides include AI (OC
H:+):+ , AI(OCzHs)s, AI(is
o-OCJ7) x, Ga(OCH3)3, Ga(O
CzHs): +, Ga (OCJv) 3, Ge (QC
)I3)s, Ge(OCJs)n, Ge(OC3H
1>a, In (0(jh) :I, In(OCzH
s) i, In (i 5o-QC: I8.) s, Nb
(OCHff)S, Nb(OC2H5)s, Nb(
OCJ7)s, 5i(OCL)4.5i(OCJs)
4.5i (iso-OC+H7), C130(Si(
OCH3)zo)acH3, Ti(OCHx)a, T
i(OCzHs)4, Ti(OCJt)4, CJ70(
Ti(OC:1H7) 20) l 0C3H? , Sn
(OCHi) 4, Sn (OCzHs) a, 5
n (iso-OCJt) a, Zr (OCf13) a
, Zr(OCzHs)a, Zr(0CJIt)4, and the like.

Further, the initial condensate of metal alkoxide can be obtained by partially hydrolyzing and polycondensing the above metal alkoxide. The degree of polycondensation (n) is generally 10 or less.

In the present invention, in the organometallic cambling agent used to form the second primer layer or the primer composition consisting of this coupling agent and PPS resin powder, the organometallic cambling agent is a silane cup. Ring agents and titanate camping agents are mainly used. These coupling agents are organometallic compounds that have in their molecules an organic group (hydrolyzable group) that binds to an inorganic substance and an organic group that has an affinity for organic substances.

Specific examples of silane coupling agents include 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(
2-aminoethyl)-3-aminopropylmethyldimethoxysilane, aminoethylaminomethylphenethyltrimethoxysilane, 1-trimethoxysilyl-2-(aminomethyl)phenylethane, 3-glycidoxypropyltrimethoxysilane, ( 3-glycidoxypropyl) methyljethoxysilane, trimethoxylylbenzoic acid, 3
-mercaptopropyltrimethoxysilane, (3-mercaptopropyl)methyldimethoxysilane, 1-trimethoxysilyl-2'-(chloromethyl)phenylethane, and the like.

Specific examples of titanate camping agents include isopropyl(N-aminoethyl-aminoethyl)tita, ethyltri(N-aminoethyl-aminoethyl)tita, and diisopropyldii(N-aminoethyl-aminoethyl). (aminoethyl) titanate, butyl tri(N-aminoethyl-aminoethyl) titanate, dibutyl di(N-aminoethyl-aminoethyl) titanate, and the like.

In addition, isobrobyl triisostearoyl titanate, tetraoctyl bis(didodecyl) phosphite titanate, isopropyltrioctanoyl titanate, isopropyl dimethacrylylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tricumylphenyl titanate,
Isopropyl tris (dioctyl pyrophosphate)
Titanate, Tetraisopropylbis(dioctylphosphite) titanate, Tetra(2,2-diallyloxymethyl-1=butyl)bis(ditridecyl)phosphite titanate, Bis(dioctylpyrophosphate)oxyacetate titanate, Bis(dioctylpyrophosphate) Examples include ethylene titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl isostearoyl diacryl titanate, and the like.

The PPS resin blended into the above coupling agent has alternating benzene-sulfur bonds, and may be partially oxidized, branched, or crosslinked.

Examples of such PPS resins include Rydon V-1 manufactured by Phillips Vetroleum and T
-4 is mentioned. Such PPS resin is used as a powder, and the particle size is preferably 300μ or less, more preferably 100D11 or less. If the particle size is as large as 300 μm or more, good dispersion in the brimer composition may not be obtained and adhesion may be reduced.

The mixing ratio of the coupling agent and the PPS resin powder is preferably in the range of 100:0 to 10:90 by weight. If the amount of PPS resin powder is too large, the adhesion between the first brimer layer and the second brimer layer to be formed will decrease.

The above-mentioned brimer composition consisting of a metal alkoxide or its initial condensate can be used as it is if it is in liquid form, but it is generally used by dissolving the metal alkoxide or its initial condensate in an organic solvent.

In addition, a coupling agent or this coupling agent and PPS
Since the coupling agent is liquid, the brimer composition consisting of resin powder can be used by simply mixing the coupling agent alone or by uniformly mixing both. used. When PPS resin powder is blended into the coupling agent, the PPS resin powder is dispersed in the solution of the coupling agent.

As the organic solvent, benzene, toluene, xylene, ethyl ether, hexyl ether, methyl ethyl ketone, n-hexane, ethanol, methanol, isopropyl ether, methyl isobutyl ketone, diethylhexanol, isopropanol, etc. are used.

Note that an inorganic filler may be added to the above-mentioned brimer compositions forming the first and second brimer layers, if necessary. Such inorganic fillers include, for example, metals,
Metal oxides, glass, carbon, ceramic inorganic salts, etc. are used.

Examples of metals include zinc, nickel alloy, stainless steel, and cast iron. Examples of metal oxides include alumina, iron oxide, titanium oxide, zirconium oxide, chromium oxide, nickel oxide, potassium titanate, talc, kaolin, clay, and mica. This includes potassium titanate. In addition to those included in metal oxides, ceramics include silicon nitride, titanium nitride, boron carbide, silicon carbide, and the like. Inorganic salts include barium sulfate.

These inorganic fillers are preferably contained in the form of fibrous, granular, or flake-like fine powder, and the average particle size is 1
The thickness is adjusted to 100 μm, preferably 5 to 30 μm.

This inorganic filler is preferably contained in an amount of 10 to 800 parts by weight, more preferably 25 to 400 parts by weight, based on 100 parts by weight of the brimer composition. If it is less than 10 parts by weight, the effect of the inorganic filler will be small, and if it exceeds 800 parts by weight, the binder ability of the brimer composition will decrease and the adhesion to the metal body will decrease.

In the present invention, first, a brimer composition made of a metal alkoxide or an initial condensate thereof is applied to the surface (surface or inner surface) of a metal body such as iron, aluminum, stainless steel, or various alloys. Next, baking is performed, and the metal alkoxide or its initial condensate is crosslinked and hardened by moisture in the air, forming a first primer layer.

The metal body has been subjected to appropriate pretreatment such as sandblasting, degreasing, and chemical conversion treatment (the temperature for baking is usually 300"C).
The temperature above is preferably 350 to 420°C. The thickness of the first primer layer is 5 to 100 μm, preferably 10 to 100 μm.
The range is 30 μm.

If it is less than 5 μm, the first primer layer will not be formed uniformly, and pinholes and cracks will likely occur. vice versa,
When it exceeds 100 μm, the adhesion between the first primer layer and the metal body decreases.

Next, an organometallic coupling agent or a primer composition consisting of the coupling agent and PPS resin powder is further applied onto the first layer of limer and baked. This causes the force/knobling agent to react, and the PP
The S resin powder is melted and hardened to form a second primer layer.

The baking temperature is usually 300"C or higher, preferably 350"C.
~420"C. The thickness of the second primer layer is
For the same reason as the first primer layer, 5 to 100 μm
, preferably in the range of 10 to 30 μm.

In addition, after applying a primer composition consisting of an alkoxide or its initial condensate to the metal surface and before baking, apply an organic metal force/knobling agent or a primer composition consisting of this coupling agent and PPS resin powder. You can apply it and then bake it all at once.

The metal body surface (surface or inner surface) on which the first primer layer and the second primer layer are formed in this order is coated with PPS resin. As this PPS resin, the same PPS resin as that used in the primer composition for forming the second primer layer is used. The coating method is PP
An electrostatic powder coating method using S resin powder is preferably employed.

After powder coating, the painted surface is baked, and the PPS resin is melted and hardened to form a resin coating layer. The baking temperature is preferably 300 to 450°C.

The thickness of the resin coating layer is 50 to 2000 μm, preferably 2
The thickness is in the range of 50 to 1000 μm. If the thickness is less than 50 um, the resin coating layer will not be formed uniformly, and pinholes and cracks will likely occur. On the other hand, if it exceeds 2000 μm, it takes time to bake, etc., and foaming occurs, making it impossible to obtain a dense resin coating layer. After baking, annealing treatment or rapid cooling may be performed.

(Function) The first primer layer formed from a primer or composition made of a metal alkoxide or an initial condensate thereof has excellent adhesion to the surface of a metal body. However, the adhesion of the PPS resin to the coating layer is generally not sufficient.

However, when a second primer layer is formed on this first primer layer using an organometallic coupling agent or a primer composition consisting of this coupling agent and PPS resin powder, the force of the pulling agent increases. It adheres well to the first primer layer due to the action of the organic group (hydrolyzable group) that binds to the inorganic substance in the molecule of the , it also adheres well to the PPS resin coating layer. Especially the second
When PPS resin is contained in the primer layer of
Adhesion with the S resin coating layer is further improved.

Further, both the first primer layer and the second primer layer have excellent heat resistance and are resistant to hot water. Therefore, it has excellent hot water resistance and the low F of adhesion under hot water is significantly reduced.

(Example) Hereinafter, Examples and Comparative Examples of the present invention will be shown.

Initial condensate of h4 metal alkoxide (B-10: manufactured by Nippon Soda Co., Ltd.) 'Cat (90 (Ti (OCJJO) + o
Csliq J was used as the primer composition for the first layer.

In addition, a silane coupling agent (SH6020: manufactured by Toshi Nlicon Co., Ltd.) 'NHzCHzCl (zNtl
(CHz) isi (OCL) 3,N(2-aminoethyl)-3-aminopropyltrimethoxysilane" was used as the brimer composition for the second layer.

After a 1100 tx x 100 mm x 3-thick iron plate was subjected to grit frust treatment, it was cleaned by blowing with compressed air, and the above-mentioned brimer composition for the first layer was applied with a brush to one side of the iron plate. The baking process was performed by drying at °C for 20 minutes. The thickness of the obtained first primer layer was 30 um on average. Next, the brimer composition for the second layer was applied with a brush on top of the first primer layer, and this was heated at 380°C for 30 um. It was dried for a minute and then baked.

The thickness of the second primer layer obtained was 30 μm on average.

PPS resin powder (T-4
(manufactured by Nidoprene Co., Ltd.) was electrostatically powder coated, and then this was coated with 3
This was baked at 80° C. for 60 minutes, poured into water, and cooled to obtain a PPS resin-coated iron plate.

The thickness of the obtained coating layer was about 700 μm.

Regarding the PPS resin-coated iron plate obtained in this way,
A normal adhesion test, a hot water resistant adhesion test, and a hot water resistant test were conducted using the following test methods.

The results are shown in Table 1.

(1) Normal adhesion test Make a 1 cm cut in the coating film of the PPS resin-coated iron plate with a sharp knife so that the cut reaches the iron plate, peel off one end, and peel it off at room temperature (23°C). speed 10 dishes 7
The peel strength was measured by pulling in a 90 degree direction for 1 minute. Note that the * mark in the table indicates that the PPS resin coating layer was broken.

(2) Hot water adhesion test After immersing a PPS resin-coated iron plate in hot water at 95°C on the coating layer side and 65°C on the iron plate side for 100 hours, cut the coating film with a sharp knife until the cut reaches the iron plate. Make a 1 cm wide cut in the strip, peel off one end, and store it at room temperature (23°).
C), the film was pulled in a 90 degree direction at a peeling speed of 10 mm/1 minute, and the peel strength was measured.

(3) Hot water resistance test After immersing a PPS resin-coated iron plate in hot water with the coating layer side at 95°C and the iron plate side at 65°C for 100 hours, the occurrence of blisters on the coating layer side was determined. Shown as area percentage.

As the primer composition for the second layer of Example 1, a silane coupling agent (SH6062 manufactured by Toshi Silicone Co., Ltd.) [5H (CHz) 3si (OCH 3,3-mercaptopropyltrimethoxysilane J) was used. 30 parts by weight,
A brimer composition prepared by uniformly mixing 70 parts by weight of PPS resin powder (Rydon Sea 1, manufactured by Philisobus Petroleum Co., Ltd.) with a particle size of 90 μm or less was used.

Other than that, the same procedure as in Example 1 was carried out.

As the second layer brimer composition of Example 1, a silane coupling agent (SH6062: manufactured by Toshi Silicone Co., Ltd.) was used.
'5H (CHz) xSi (OCt13> 3.3
- PPS resin powder with a particle size of 90 μm or less (Rydon Sea 1
A brimer composition prepared by uniformly mixing 10 parts by weight of 10 parts by weight (manufactured by Filimbs Veterolium Co., Ltd.) was used.

Other than that, the same procedure as in Example 1 was carried out.

A titanate-based cambling agent (Plenact K11144: manufactured by Ajinomoto Co., Ltd.) 'CJ70Ti (OCz) IJHCzH4N was used as the second layer brimer composition of SJ1 Special Earth Example 1.
Hz) 3, 30 parts by weight of isopropyltri(N-aminoethyl-aminoethyl) titanate was uniformly mixed with 70 parts by weight of PPS resin powder with a particle size of 9 Gμm or less (Rydon Thor 1, manufactured by Filimbs Veterolium). A brimer composition consisting of: Other than that, the same procedure as in Example 1 was carried out.

As the primer composition for the first layer of Example 1, a composition consisting of metal alkoxide [Zr (OC4H9) 4: (manufactured by Nippon Soda Co., Ltd.)] was used. In addition, as a primer composition for the second layer, a titanate-based cambling agent (Plenac l-KR44: manufactured by Ajinomoto Co., Ltd.) "C: +H70T
i (OCzLNHCJJl+□)3, isopropyltri(N-aminoethyl-amineethyl)titanate"3
A brimer composition was used in which 70 parts by weight of PPS resin powder (Rydon v-1, manufactured by Phillips Petroleum Co., Ltd.) having a particle size of 90 μm or less was uniformly mixed with 0 parts by weight. Other than that, the same procedure as in Example 1 was carried out.

As the first layer brimer composition of Example 1, Metal Alkoxide'AI (OCJ?) 4: (manufactured by Nippon Soda Co., Ltd.)
A composition consisting of j was used. In addition, as a primer composition for the second layer, a titanate coupling agent (Brenact KR44: manufactured by Ajinomoto Co., Ltd.)'C:l)+7071 (
OCJ4NHCJaNHz) 3. Isopropyl tri(
N-aminoethyl-aminoethyl) titanate J 30
A brimer composition was used in which 70 parts by weight of PPS resin powder (Rydon v-1, manufactured by Philips Vetroleum Co., Ltd.) having a particle size of 90 uI11 or less was uniformly mixed with 70 parts by weight. Other than that, the same procedure as in Example 1 was carried out.

For comparison, Example 1 was carried out in the same manner as in Example 1, except that neither the first layer nor the second layer brimer compositions were applied.

The same procedure as in Example 1 was carried out except that the brimer composition for the first layer of peeling strip was not applied.

Comparison I The same procedure as in Example 1 was carried out except that the second layer primer composition was not applied.

Table 1 (Effects of the Invention) As mentioned above, the PPS resin-coated metal body of the present invention has a first primer layer formed on the surface of the metal body by a brimer composition made of a metal alkoxide or an initial condensate thereof,
A second primer layer is formed thereon by a primer composition consisting of an organometallic coupling agent or this combing agent and PPS resin powder, and a PPS resin is coated thereon. According to the method, a resin-coated metal body having excellent heat resistance, excellent adhesion between the coated PPS resin and the metal body, and particularly good hot water resistance can be obtained.

Therefore, the PPS resin-coated metal body of the present invention is useful for corrosion protection of metal surfaces that come into contact with hot water, such as vibrators and joints for hot water supply.
It can be suitably used for pipes and joints in chemical plants.

Claims (1)

[Claims] 1. A first primer layer made of a primer composition made of a metal alkoxide or an initial condensate thereof is formed on the surface of the metal body, and a first primer layer made of an organometallic coupling agent or this coupling agent and polyphenylene sulfide resin powder is formed on the first primer layer. A polyphenylene sulfide resin-coated metal body, characterized in that a second primer layer is formed using a primer composition, and a polyphenylene sulfide resin is coated thereon.