JPS62172046A - Vinylidene fluoride based composite material - Google Patents

Abstract

PURPOSE:A vinylidene fluoride based composite material, obtained by coating a metal substrate with a composition containing vinylidene fluoride resin previously irradiated with ionizing radiation and an organosilicon compound and having good adhesive property to the metal substrate. CONSTITUTION:A composite material obtained by blending (A) 100pts.wt. vinylidene fluoride resin irradiated with ionizing radiation, (one or more of beta-rays-, gamma-rays, alpha-rays, neutron rays X-rays and accelerated electron rays, preferably gamma-rays or accelerated electron rays) at >=0.1 Mrad with (B) 0.1-10pts.wt. organosilicon compound expressed by the formula (R is olefinic hydrocarbon group; Y is hydrolyzable organic group; R' is R or Y). e.g., vinyltrimethoxysilane or vinyltriethoxysilane, etc., and preferably (C) <=300pts.wt. organic filler, e.g. powder of a thermosetting resin, etc., and/or inorganic filler, e.g. talc, mica, etc., melt kneading the resultant blend and coating a metal substrate with the resultant composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a vinylidene fluoride composite material in which a vinylidene fluoride resin and a metal substrate are firmly bonded.

(Conventional technology) Vinylidene fluoride resin has excellent chemical resistance, heat resistance, and weather resistance, and can be easily molded at relatively low temperatures. It is widely used as a laminated composite material. However, vinylidene fluoride resin has particularly poor adhesion to metal materials, which makes it difficult to form a practical composite material.

In order to improve the adhesion of vinylidene fluoride resin to metal materials, Japanese Patent Application Laid-Open No. 52-51479 discloses.

After etching aluminum or aluminum alloy and coating it with fluororesin dispersion.

Furthermore, a method for hot-pressing a fluororesin film is disclosed. However, this method requires complicated steps.

Chromium ion is disclosed in Japanese Unexamined Patent Publication No. 55-61961.

A primer consisting of an aqueous dispersion of vinylidene fluoride resin containing hydrogen ions is applied to the metal surface.
A method is disclosed in which vinylidene fluoride resin powder is adhered thereon and then heated and sintered. But this method also. Not only is the process complicated, but the resulting composite material has pinholes that are typical of powder coating.

In order to solve these drawbacks, Japanese Patent Application Laid-Open No. 56-133
Publication No. 309 discloses a composite material in which an acrylic acid or methacrylic acid polymer is graft-bonded to a vinylidene fluoride resin, and the graft is bonded to a metal. Although this material has a strong bond between the vinylidene fluoride resin and the metal, it requires a grafting process of the vinylidene fluoride resin to form the resin material. To prevent the formation of
Grafting must be done in the presence of water containing a chain inhibitor such as copper sulfate or ferrous sulfate.

Such operations are complicated.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to use a vinylidene fluoride resin that has good adhesive properties between vinylidene fluoride resin and a metal substrate. Our goal is to provide composite materials. Another object of the present invention is to provide a vinylidene fluoride composite material that can be easily obtained by a common melt molding method such as extrusion molding.

(Means for Solving the Problems) The present invention involves graft polymerizing an organosilicon compound to a vinylidene fluoride resin that has been irradiated with ionizing radiation in advance, and coating the grafted vinylidene fluoride resin on a metal substrate. Through this process, a vinylidene fluoride composite material in which resin and metal are firmly bonded can be obtained through a simple process. It was completed based on the inventor's knowledge.

The vinylidene fluoride composite material of the present invention is obtained by coating a metal substrate with a composition containing a vinylidene fluoride resin that has been irradiated with ionizing radiation in advance and an organosilicon compound represented by the following formula. The purpose is achieved.

here.

R is an olefinic hydrocarbon group.

Y is a hydrolyzable organic group 2 and Ro is R or Y.

Other vinylidene fluoride composite materials of the present invention include:

The above object is achieved by coating a metal substrate with a composition obtained by adding an organic filler and/or a non-filler to the above composition.

Vinylidene fluoride resin refers to vinylidene fluoride homopolymers and copolymers of vinylidene fluoride and other monomers. As a monomer, ethylene.

Propylene, vinyl chloride, tetrafluoroethylene, dichlorofluoroethylene, 1,1,2-trifluoro-
There are halogenated ethylenes such as 2-chloroethylene.

Such monomers are contained in the copolymer in a proportion of 5 mol% or less.

If it exceeds 5 mol%, the properties of the vinylidene fluoride resin will be impaired. Commercially available products include KF Polymer (manufactured by Kureha Chemical Co., Ltd.) and Kynar (manufactured by Pennwalt Co., Ltd.).

Ionizing radiation includes 2 e.g. β rays, γ rays, and cX rays.

There are neutron beams, X-rays, accelerated electron beams, and especially gamma rays.

An accelerated electron beam is preferred. Gamma rays are preferable for granular vinylidene fluoride resin. After a sheet of vinylidene fluoride resin is continuously irradiated with an electron beam, it is formed into a pellet. The radiation dose is said to be 0.1 megaland or more. If it is less than 0.1 megaland, the desired adhesion to metal cannot be obtained even if an organosilicon compound is added and mixed in a subsequent step. Although there is no particular limit to the maximum dose, if a large amount of irradiation is applied, vinylidene fluoride resin will decompose.

As a result, the resin becomes colored and deteriorates, which is undesirable.

Organosilicon compounds have 2 alkoxy groups, acyloxy groups,
It contains hydrolyzable organic groups such as oxime groups and substituted amine groups and olefinic hydrocarbon groups. For such organosilicon compounds.

Examples include vinyltrimethoxysilane and vinyltriethoxysilane. The organosilicon compound is contained in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of vinylidene fluoride resin. If it is less than 0.1 part by weight, desired adhesion to metal cannot be obtained. 1
If the weight exceeds 0 weight, the adhesion will not improve so much and the properties of the vinylidene fluoride resin will be impaired.

As the metal substrate, any known metal can be used, 9 such as aluminum and its alloys, iron and its alloys, stainless steel, aluminum and its alloys. The surface of metal substrates is exposed to acids, alkalis, and detergents.

Surface treatments such as chemical conversion treatment and oxidation treatment, which are preferably washed with an organic solvent or the like, may be performed. Also,
Blasting, sand vapor treatment, plating, thermal spraying, etc. may be applied.

However, conventional etching and treatment with vinylidene fluoride primer are not necessary.

The shape of the metal substrate is arbitrary, and in particular, if it is tubular, a composite tube with excellent chemical resistance, heat resistance, weather resistance, and adhesiveness can be obtained.

The vinylidene fluoride composite material of the present invention is obtained by melt-kneading a vinylidene fluoride resin and an organosilicon compound that have been irradiated with ionizing radiation in advance, and directly coating a metal substrate with the kneaded product. For melt mixing, use an axle or twin-shaft pusher.

A kneading machine such as a Banbury mixer is used.

The kneading temperature is preferably 150 to 250°C. If the temperature drops below 150℃, vinylidene fluoride resin will not melt.
Kneading of the vinylidene fluoride resin and the organosilicon compound becomes insufficient. If the temperature exceeds 250°C, the vinylidene fluoride resin becomes noticeably colored during melt-kneading, and the decomposition reaction is accelerated, thereby generating toxic substances such as hydrofluoric acid. Although the kneading time is not particularly limited, if kneading is continued for too long, the vinylidene fluoride resin will decompose. The melt-kneaded product may be once cooled and solidified to form granules, and then melt-kneaded again as it is or with additives such as an antioxidant or an ultraviolet absorber added thereto, and then coated on a metal substrate.

When the composite material of the present invention is made into a composite tube using a tubular metal substrate, a powder coating method is used in which the metal tube is sprayed with a molten kneaded material containing a vinylidene fluoride resin and an organosilicon compound that has been irradiated with ionizing radiation in advance. Alternatively, there is a lining method in which a kneaded material is made into a film or sheet and lined onto a metal tube. In either method, a composite tube in which the vinylidene fluoride resin and the metal substrate are firmly bonded can be obtained. In the manufacture of composite pipes, the surface of the metal pipe is coated with resin by continuously applying a belt-shaped excess pressure. The outer surface of the metal tube may be coated with resin if necessary.

An organic or inorganic filler may be further added to the composite material of the present invention in order to improve adhesion to metal. Vinylidene fluoride resin has a large linear expansion Ff, and therefore adhesiveness decreases due to the difference in linear expansion coefficient with metal. The linear expansion coefficient of 27vinylidene fluoride resin is (0,7
~1.5) x]O-'/'c, aluminum is 0.23 x 10-'/'c, and iron is 0.11 x 10-'/'C. In particular, vinylidene fluoride After coating the melted and kneaded resin onto the metal substrate.

When cooled, resin tends to peel off. Therefore, the organic or inorganic filler is preferably a substance that lowers the coefficient of linear expansion of the vinylidene fluoride resin. Examples of organic fillers include powders of thermosetting resins such as phenolic resins and melamine resins, organic fibers such as carbon fibers and aramid fibers, and graphite wood powder. Examples of inorganic fillers include fine inorganic powders such as talc, mica, and calcium carbonate, and inorganic fibers such as glass fibers and potassium titanate fibers. The organic or inorganic filler is added in an amount of 300 parts by weight or less, preferably 5 to 100 parts by weight, per 100 parts by weight of the vinylidene fluoride resin. 3
If it exceeds 0.00 parts by weight, the properties of the vinylidene fluoride resin will be impaired. The filler may be added either during mixing or during melt-kneading.

(Example) The present invention will be described below with reference to examples.

Vinylidene fluoride resin powder (KF Polymer" 1100)
(manufactured by Kureha Kagaku Co., Ltd.) in a polyethylene container.

γ-rays (60Co) were irradiated at 1.0 megaland in air.

To 100 parts by weight of this T-ray irradiated vinylidene fluoride resin, 2.0 parts by weight of vinyltrimethoxysilane (VTS-M, manufactured by Chisso Corporation) was added and mixed for 5 minutes using a Henschel mixer. Pour the mixture into cylinder part 220°C1 mold 2
Extrusion was performed at a temperature of 00° C. using a twin-screw extruder with a diameter of 30 m5 to obtain a pellet-shaped vinylidene fluoride resin composition. An aluminum plate (aluminum 3004-0 material, manufactured by Sumitomo Light Metal Co., Ltd., thickness 0.25 mm) was heated at 50°C for 10 minutes.
% sodium hydroxide solution, the above resin composition was placed on the surface.

After preheating this at 220℃ for 3 minutes, 10kg/cn
! When pressed for 1 minute at a pressure of 1 mm, the thickness was 1 mm.
A 20 cm square vinylidene fluoride-aluminum laminate having a vinylidene fluoride resin layer was obtained. When this laminate was subjected to a 180 degree I peel test (an aluminum plate was peeled off at a 180 degree angle to the vinylidene fluoride resin layer), it was found that the center part was 7 degrees 8 kg/2 cm (middle 2
A peel strength of (adhesion force per cm) was obtained. These results are shown in the table below.

A vinylidene fluoride-aluminum laminate was obtained in the same manner as in Example 1, except that 0.8 parts by weight of the bulk vinyltrimethoxysilane was used. When this laminate was subjected to a 180 degree Ml peel test in the same manner as in Example 1, a peel strength of 4.5 kg/2 cm was obtained at the center. These results are shown in the table below.

A vinylidene fluoride-aluminum laminate was obtained in the same manner as in Example 1, except that 0.8 parts by weight of the acrylvinyltrimethoxysilane and the γ-ray irradiation dose were 3.0 Megaland. About this laminate.

When a 180 degree peel test was conducted in the same manner as in Example 1, a peel strength of 5.2 kg/2 cjn was obtained at the center. These results are shown in the table below.

Example 4 Except that the γ-ray irradiation dose was 3.0 megaland,
A vinylidene difluoride-aluminum laminate was obtained in the same manner as in Example 1. About this laminate.

When a 180 degree peel test was conducted in the same manner as in Example 1, a peel strength of 8.0 kg 72 cm was obtained at the center. These results are shown in the table below.

Comparative Example I An attempt was made to produce a vinylidene fluoride-aluminum laminate in the same manner as in Example 1, except that γ-rays were not irradiated. However, the vinyl-11dene fluoride resin did not adhere to the aluminum plate at all. These results are shown in the table below.

Comparison 1 Except that vinyltrimethoxysilane was not used.
A vinylidene fluoride-aluminum laminate was obtained in the same manner as in Example 1. This laminate was prepared in the same manner as in Example 1 to obtain a 180 degree angle. , ++ When a separation test was performed,
Only a peeling strength of 0.6 kg/2CI, 7 l was obtained in the central part. These results are shown in the table below.

几(U-1) Except that vinyltrimethoxysilane was not used,
A vinylidene fluoride-aluminum laminate was obtained in the same manner as in Example 3. When this laminate was subjected to a 180 degree peel test in the same manner as in Example 1, a peel strength of only 0.7 kg/2 cm was obtained at the center. These results are shown in the table below.

Vinylidene fluoride-
An aluminum laminate was obtained. When this laminate was subjected to a 180 degree peel test in the same manner as in Example 1, a peel strength of 8.3 kg/2 cm was obtained at the center.

Except that a 0.15 mm thick iron plate was used instead of the aluminum plate, and this was treated with a 10% nitric acid solution.

A vinylidene fluoride-iron laminate was obtained in the same manner as in Example 1. A 180 degree peel test was conducted on this laminate using the same method as in Example 1.

A II separation strength of 5.5 kg/2 cIIl was obtained at the center.

Example 7 A copper plate with a thickness of 0.10 mm was used in place of the aluminum plate, except that this was treated with a 10% nitric acid solution.

A vinylidene fluoride-copper laminate was obtained in the same manner as in Example 1. A 180 degree peel test was conducted on this laminate using the same method as in Example 1.

A peel strength of 5.6 kg/2 am was obtained at the center.

A gamma-ray irradiated vinylidene fluoride resin mixture obtained in the same manner as in Example 1 was molded into a cylinder part 230"C1 mold 210".
A single screw extruder (width 150 m) with a diameter of 65 φ at a temperature of 'e
n, equipped with a fishtail die with an opening of 0.6 mm thickness).

The extruded film-like melt was transferred onto a strip-shaped aluminum temporary (aluminum @ 5052° manufactured by Sumitomo Light Metal Co., Ltd., thickness 0.2 mm, medium 200 m) preheated to 230°C using the pressure roll device shown in Figure 5. was continuously coated and crimped. When crimped at a crimping speed of 3 m/min,
A vinylidene fluoride-aluminum laminate having a vinylidene fluoride resin layer with a thickness of 0.5 mm was obtained. A 180 degree peel test was conducted on the center and 4011 points from the ends in the same manner as in Example 1, and the peel strength was 1-5 kg/2 clll at the center and 4011 points from the ends. , 1 kg/2 c
A peel strength of m was obtained.

Example 8 except that 10 parts by weight of mica (Sujirite Mica" 2001+, manufactured by Kuraray Co., Ltd.) was added to 100 parts by weight of vinylidene fluoride resin in the γ-ray irradiated vinylidene fluoride resin mixture. A vinylidene fluoride-aluminum laminate was obtained in the same manner as above.The central part of this laminate and a portion 4011 from the edge were obtained.

When a 180 degree peel test was conducted in the same manner as in Example 1, the weight was 7.3 kg/2 crn at the center and 5.8 kg/2 cm at the 40 mm distance from the edge.
A peel strength of .

Example 10 The same procedure as Example 8 was carried out, except that 30 parts by weight of mica (Sujirite Mica 1120011, manufactured by Kuraray Co., Ltd.) was added to 100 parts by weight of vinylidene monofluoride resin in the γ-ray irradiated vinylidene fluoride resin mixture. Vinylidene fluoride
An aluminum laminate was obtained. About the central part and the part 4Q+n from the edge of this laminate.

A 180 degree H111 separation test was conducted in the same manner as in Example 1, and the result was 7-Okg/2 cm at the center.
And 6.9kg/2cm work 1 at 40m from the end.
A separation strength of 1 was obtained.

As is clear from the Examples and Comparative Examples, the vinylidene fluoride composite material of the present invention has good adhesion to metal substrates, and also shows high values in the 180 degree peel test. Adhesion can be further improved by surface-treating the metal substrate in advance.

Furthermore, the adhesion of the composite material to which 1 mica is added is significantly improved near the edges. Vinylidene fluoride composite materials that do not contain vinyltrimethoxysilane or vinylidene fluoride composite materials that are not irradiated with gamma rays do not adhere to metal substrates at all or exhibit almost no adhesive properties.

(Effects of the invention) The vinylidene fluoride composite material of the present invention is thus:
It is easily obtained and has good adhesion between the vinylidene fluoride resin and the metal substrate. Therefore.

Improves corrosion resistance of metals. The composite material of the present invention is.

Therefore, it can be effectively used to protect the metals of products used outdoors, such as household equipment.

1-"Force 1Δ"] The CL diagram is an explanatory diagram showing one embodiment of the apparatus used for manufacturing the composite material of the present invention.

DESCRIPTION OF SYMBOLS 1... Single-screw extruder, 2... Molten vinylidene fluoride resin, 3... Temporary aluminum band, 4... Pressing roll.

10...Fishieter die.

that's all

Claims (1)

[Scope of Claims] 1. A vinylidene fluoride composite material obtained by coating a metal substrate with a composition containing a vinylidene fluoride resin that has been irradiated with ionizing radiation in advance and an organosilicon compound represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R is an olefinic hydrocarbon group, Y is a hydrolyzable organic group, and R' is R or Y. 2. The vinylidene fluoride composite material according to claim 1, wherein the organosilicon compound is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the vinylidene fluoride resin. 3. The vinylidene fluoride composite material according to claim 1, wherein the dose of the ionizing radiation is 0.1 megarad or more. 4. The vinylidene fluoride composite material according to claim 1, wherein the organosilicon compound is at least one of vinyltrimethoxysilane and vinyltriethoxysilane. 5. The vinylidene fluoride composite material according to claim 1, wherein the ionizing radiation is at least one of β rays, γ rays, α rays, neutron beams, X rays, and accelerated electron beams. 6. Vinylidene fluoride obtained by coating a metal substrate with a composition containing a vinylidene fluoride resin pre-irradiated with ionizing radiation, an organosilicon compound represented by the following formula, and an organic filler and/or an inorganic filler. system composite material. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R is an olefinic hydrocarbon group, Y is a hydrolyzable organic group, and R' is R or Y. 7. The vinylidene fluoride composite material according to claim 6, wherein the organosilicon compound is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the vinylidene fluoride resin. 8. The vinylidene fluoride composite material according to claim 6, wherein the dose of the ionizing radiation is 0.1 megarad or more. 9. The vinylidene fluoride composite material according to claim 6, wherein the organosilicon compound is at least one of vinyltrimethoxysilane and vinyltriethoxysilane. 10. The vinylidene fluoride composite material according to claim 6, wherein the ionizing radiation is at least one of β rays, γ rays, α rays, neutron beams, X-rays, and accelerated electron beams. 11. For 100 parts by weight of the vinylidene fluoride resin,
The vinylidene fluoride composite material according to claim 6, wherein the organic filler and/or inorganic filler is contained in a proportion of 300 parts by weight or less. 12. Claim 6, wherein the organic filler is at least one of thermosetting resin powder such as phenolic resin and melamine resin, organic fiber such as carbon fiber and aramid fiber, graphite, and wood flour. Vinylidene fluoride composite material described in . 13. The fluoride according to claim 6, wherein the inorganic filler is at least one of inorganic fine powders such as talc, mica, and calcium carbonate, inorganic fibers such as potassium titanate fibers, and glass fibers. Vinylidene composite material.