JPS60124245A - Laminate having excellent weather resistance - 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 [I] Object of the Invention The present invention relates to an A-layer material having good weather resistance and having a metal layer as an intermediate layer. More specifically, it is a laminate formed by laminating (A) a metal layer having a coating layer with good weather resistance and (B) an inorganic filler-containing olefin polymer layer, and the thickness of the coating layer is The thickness of the metal layer is 5 microns to 1 mm, and the thickness of the inorganic filler layer is 500 microns to 1 mm.
5 mm, and the content of inorganic filler 111 in this layer is 10
This relates to a laminate with good weather resistance characterized by a content of 80% by weight, and the object thereof is to provide a radio wave reflective laminate in which a metal layer serving as an intermediate layer reflects radio waves.

[+1] Behind the invention? Conventionally, metal plates or metal nets have been used as radio wave reflecting plates. However, since metals corrode, it is necessary to make them into anti-corrosive alloys or apply anti-corrosive coatings. However, anti-corrosion alloys are expensive, and anti-corrosion coatings also have the problem of being expensive because it is necessary to apply them several times to achieve complete corrosion protection. Even if this is done, corrosion will gradually progress with long-term use. Furthermore, attempts have been made to manufacture radio wave reflectors in which glass fibers with metallized surfaces are laminated to thermoplastic resins such as unsaturated polyester resins, but the manufacturing method is cumbersome and It has been extremely difficult to maintain the radio wave reflective layer at a constant thickness and without unevenness.

[111] Structure of the Invention Based on the above, the present inventors have conducted various searches to obtain a laminate that has a simple manufacturing process, has radio wave reflecting ability, and can maintain its performance for a long period of time. As a result, a laminate consisting of at least (A) a metal layer having a coating layer with good weatherability and (B) an inorganic filler-containing olefin polymer layer is obtained, and the thickness of the coating layer is is 5 microns to 1IIIll, the thickness of the metal layer is 5 microns to 1+on+, and the thickness of the inorganic filler-containing olefin polymer layer is 500 microns to 15 microns, and the thickness of the inorganic filler in this layer is 500 microns to 15 microns. Content is 10-80% by weight
The inventors have discovered that a laminate with good weather resistance characterized by the following characteristics not only has good durability but also has excellent radio wave reflection properties, and has thus arrived at the present invention.

[IV] Effects of the invention The laminate of the invention exhibits the following effects (features) including its manufacturing process.

(1) Since it has excellent corrosion resistance, there is no change in radio wave reflection characteristics over a long period of time.

(2) The difference in linear expansion coefficient between the metal layer and the inorganic filler-containing olefin polymer layer is extremely small, so even if subjected to heat cycles (repetitive cold and heat) for a long time, no delamination will occur between the layers. .

(3) The laminate is light J6 and the manufacturing process is simple.

(4) The metal layer can be formed uniformly,
There is no uneven reflection of radio waves.

(5) Inorganic filler-containing olefin polymers can be easily formed into various complex shapes, and therefore can be used as parts that require good appearance and functionality.

(8) The laminate has excellent mechanical strength (especially rigidity) and can be used as a structure.

Since the laminate obtained by the present invention has the above-mentioned effects, it can be used in a wide range of fields as a radio wave reflector.

[V] Detailed Description of the Invention (A) Coating 4 The coating used for manufacturing the metal layer having a coating layer with good weather resistance of the present invention is widely produced industrially, and is used as a coating for metal. It is used in many different ways. The manufacturing method and various physical properties of these paints are well known. These paints are classified into solvent type using organic solvents such as toluene and xylene, aqueous emulsion type, and solvent-free type, but any type of paint can be selected depending on the coating method. Typical examples of these paints include unsaturated or saturated polyester resin paints, polyurethane resin paints obtained by reacting polyester polyols, polyether polyols, or polyurethane polyols with diisocyanates, aminoalkyd resin paints, Acrylic resin paint, melamine resin paint, cyanoacrylate-1 resin paint, epoxy resin paint, silicone resin paint, organic titanate paint 1M polyamide resin paint, acrylic urethane resin paint, acrylic resin paint and fluorine-containing resin paints such as polyvinylidene resin. Furthermore, additives such as matting agents such as silicic acid, coloring agents such as pigments and dyes, butylation inhibitors, and ultraviolet absorbers can be added to these paints. Among the above paints, polyurethane resin paints, acrylic resin paints, epoxy resin paints, amide/alkyd resin paints, and vinylidene fluoride resin paints are preferred because of their excellent weather resistance. Particularly, by incorporating an antioxidant and an ultraviolet absorber into the paint of the present invention, a paint with good weather resistance can be obtained, which is suitable.

(B) Metal layer Furthermore, representative examples of metals that are raw materials for the metal layer in the present invention include metal carriers such as aluminum, iron, nickel, copper, and zinc, and alloys containing these metals as main components (for example, stainless steel). steel, brass). These metals do not need to be surface-treated, and may be previously subjected to surface treatment such as chemical treatment or plating treatment. Furthermore, those that have been painted or printed can also be preferably used.

(C) Olefin polymer The olefin polymer used for producing the inorganic-containing olefin polymer layer in the present invention includes:
homopolymers of ethylene or homopolymers of propylene,
Copolymers of ethylene and propylene; copolymers of ethylene and/or propylene with other α-olefins having at most 12 carbon atoms (copolymerization ratio of α-olefins is at most 20% by weight). . The melt index of these olefin polymers (JIS K-876
According to 0, the temperature is 180°C and the load is 2.18
kg, hereinafter referred to as "ni,
Measured under the following conditions, hereinafter referred to as MFIJ: 0.01~
ioog/10 minutes is preferable, especially 0.02~
80 g/10 minutes is preferred.

M, 1. Alternatively, if an olefin polymer having 14F+ of less than 0.01 g/10 min is used, the moldability of the resulting mixture is poor. -) If an olefin polymer with a weight exceeding +00 g/10 minutes is used, the mechanical properties of the resulting molded product will be poor. In addition, low sparrow degree (0,900g
/ crn') or high density (0,980 g/c
m') ethylene homopolymer or ethylene and a small amount
A copolymer with the above-mentioned α-olefin, a propylene homopolymer, or a random or block copolymer of propylene with ethylene and/or other α-olefin is desirable.

These olefin polymers have a catalyst system (so-called Ziegler catalyst) made of a transition metal compound and an aluminum compound, and a chromium-containing compound (e.g., oxide float) supported on a carrier (e.g., silica). It is obtained by homopolymerization or copolymerization of olefins using catalyst systems obtained by (so-called Phillips catalysts) or radical initiators (for example, organic peroxides).

Furthermore, in the present invention, modified polyolefins obtained by graft polymerizing a compound having at least one double bond (for example, an unsaturated carboxylic acid, a base carboxylic acid, a vinyl silane compound) to these olefin polymers are also used. included.

The methods for producing these olefin resins and modified polyolefins are well known.

These olefin polymers and modified polyolefins may be used alone or in combinations of two or more J, = 4
11 may be used. Furthermore, two or more of these olefin polymers and modified polyolefins may be used as a resin blend in any proportion.

(D) Inorganic filler The inorganic filler used to produce the olefinic polymer layer containing the I@organic filler is generally one widely used in the fields of synthetic resins and rubber. These inorganic fillers are preferably inorganic compounds that do not react with oxygen and water and do not decompose during kneading and molding. As the inorganic filler,
Metal oxides such as aluminium, copper, iron, lead and nickel, gold-14 and metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony and titanium, their hydrates (hydroxides) ), compounds such as sulfates, carbonates, silicates,
It is broadly classified into these double salts and mixtures thereof. Typical examples of the inorganic filler include the metals mentioned above, aluminum oxide (alumina), its hydrate, calcium hydroxide,
Magnesium liquefied (magnesia), magnesium hydroxide, tin oxide (lead (zinc mushroom), red lead and lead mortar), magnesium carbonate, calcium carbonate, basic magnesium carbonate, white carbonate, asbestos I.
, mica, curcum, glass fiber, glass powder, glass peas, clay, algae, silica, wollastoniton, titanium oxide (titania), lithopone, pumice grains, aluminum sulfate (gypsum, etc.), zirconium acid, zirconium oxide, Examples include barium carbonate, dolomite, molybdenum disulfide, and iron sand. Among these inorganic fillers, those in powder form have a diameter of fm or less (preferably 0.5
mm or less) is preferable. In addition, in fibrous materials,
The diameter is 1 to 500 microns, preferably 1 to 300 microns.
microns) and has a length of 0.1 to E1 mm (preferably 0.1 to 5 mm). moreover,
It is preferable that the flat plate-like material has a diameter of 2 mm or less (preferably 1+nm or less).

(E) Structure of each layer (+) Coating layer The coating layer of the present invention serves to prevent corrosion of the metal layer. From these things, I got excited.

The diameter is between 5 microns and 1 mm, preferably between 10 microns and 0.5 mm, especially between 10 microns and 0.5 mm.
.

3 mm is preferred. If the thickness of this coating layer is less than 5 microns, not only will the metal layer corrode, but it will also be used! Due to contact and friction with other items at j,
There is a problem in that the metal layer may become exposed due to wear. On the other hand, if it exceeds 5 mm, not only will the reflectance of radio waves decrease, but it will also increase the cost of the laminate. Undesirable for increasing or increasing.

(2) Metal layer The metal layer of the present invention serves to reflect radio waves. The thickness of this metal layer is between 5 microns and 1 mm;
5 to 500 microns is preferred, especially 10 to 5
00 microns is suitable for women. If the thickness of the metal layer is less than 5 microns, the metal layer is likely to wrinkle or fold during the production of a laminate, causing problems in terms of appearance and performance. On the other hand, if it exceeds 1 mm, not only will the weight increase, but the cost will also increase, and this will cause problems when bending or bending the laminate.

(3) Inorganic filler-containing olefin polymer layer The composition ratio of the inorganic filler in the inorganic filler-containing olefin polymer layer of the present invention is 10 to 80% by weight (i.e., the composition of the olefin polymer The proportion is 90-20% by weight), 1
Preferably 0 to 70 weight h1%.

In particular, 10 to 60% by weight is suitable. If the composition ratio of the inorganic filler in the inorganic filler-containing olefin polymer layer is less than 10 stars, the linear expansion coefficient of the inorganic filler-containing olefin polymer layer will be too different from that of the metal layer, resulting in heat resistance. There is a problem that not only is there a possibility that spalling occurs between the metal layer and the inorganic filler-containing olefinic polymer layer due to the cycle, but also that the resulting laminate lacks rigidity. If the force exceeds 80% by weight, it is difficult to produce a homogeneous composition, and even if a homogeneous composition is obtained, it will be laminated in sheet production and injection molding as described below. When manufacturing products, it is not possible to obtain good products (laminates).

The thickness of this inorganic filler-containing olefin polymer layer is 5
00 microns to 15 mm, preferably 1 to 10 mm, especially 1 to 7 mm. If the thickness of the inorganic filler-containing olefin polymer layer is less than 500 microns, it is undesirable because it lacks rigidity and is easily deformed and damaged by external forces. On the other hand, if it exceeds 15 mm, it will take time to cool down during molding, and not only will sink marks be more likely to occur on the surface, but the weight will increase, causing problems in use.

In producing the inorganic filler-containing olefin polymer layer, stabilizers against oxygen, heat and ultraviolet rays, metal deterioration inhibitors, which are commonly used in the respective fields,
Flame retardant, colorant, electrical property improver, antistatic agent, 1
Additives such as aggregate, additives, property improvers, and tack improvers are added to the extent that they do not impair the properties of the compositions of the thermoplastic resin layer and inorganic filler-containing olefin-based composite layer of the present invention. You may.

When producing the inorganic filler-containing olefin polymer of the present invention (including when the above additives are blended), a mixer such as a Henschel mixer, which is commonly used in each industry, is used to drive and dry the olefin polymer. It can be obtained by melt-kneading using a mixer such as a Banbury mixer, Nigu, roll mill, or screw extruder. At this time, a homogeneous composition (compound) can be obtained by tri-blending in advance and melt-kneading the resulting composition (mixture). In this case, the shells are melt-kneaded and then formed into pellets, which are then subjected to the forming described later.

When melt-kneading is carried out in the production of the above-mentioned blends, it must be carried out at a temperature higher than the melting point or softening point of the olefin polymer used, but if carried out at a high temperature... The combination deteriorates. For these reasons, the temperature is generally 20°C higher than the melting point or softening point of the olefin polymer (preferably higher than 50°C), but it is carried out within a temperature range that does not cause deterioration. .

(F) Manufacture of laminate The v1 layered product obtained by the present invention is as follows (
It consists of A) a metal layer having a coating layer and (B) an olefinic polymer layer containing an inorganic filler.

The laminate obtained by the present invention will be explained in more detail with reference to FIG. FIG. 1 is a partially enlarged sectional view of a laminate in which a metal layer and an inorganic filler-containing olefin-based polymer are laminated, looking at the 19th coating layer.

In FIG. 1, A is a coating layer and B is a metal layer. Further, C is an olefin polymer layer containing an inorganic filler. The laminate of the present invention is composed of a metal layer and a filler-containing olefin-based composite layer, which form a coating layer. If the adhesion between the two layers is good, it may be used as is, but if the adhesion is poor, the adhesion (v: adhesion) between them should be sufficiently increased. An adhesive agent such as a primer may be used to maintain the adhesive properties. There are various methods for producing the laminate of the present invention. A typical example of this method is to apply an adhesion promoter or primer to one side of the metal layer and dry it, then apply a paint (-) to form a metal layer with a coating layer containing an inorganic filler as shown below. It may be laminated with an olefin polymer layer.Also, after laminating the metal layer and the inorganic filler-containing olefin polymer layer, a paint may be applied to the upper surface of the metal layer.Metal with a coating layer To laminate an inorganic filler-containing olefin polymer layer on the 4119 layer or 4119 layer, insert the inorganic filler into the mold of an injection molding machine in advance on one side of the metal layer or on the other side that does not have a coating layer. It can also be produced by injection molding an agent-containing olefin polymer.

In any of these methods, if the adhesion between the metal layer and the inorganic filler-containing olefin polymer layer is excellent, molding can be performed by these methods without applying an adhesion promoter to the metal layer. A laminate may also be produced by Also,
A laminate may be produced by bonding the metal layer and the inorganic filler-containing olefin polymer layer in advance by extrusion lamination, Luless molding, or insert injection molding with or without the intervention of an adhesion agent. Furthermore, a metal layer with or without a coating layer and an inorganic filler-containing olefin polymer layer are laminated in this order with or without an adhesion promoter between the respective layers, It may also be manufactured by heat-pressing.

None of the above extrusion lamination method, press molding method, insert injection molding method, and thermocompression bonding method is a modification of the present invention, and any commonly used method may be applied. When heating in these methods, it goes without saying that the heating must be carried out within a temperature range in which the inorganic filler-containing olefin polymer used does not undergo thermal deterioration. These methods for producing the VT layer are merely some examples, and other methods may be applied.

[VI] Examples and Comparative Examples The present invention will be explained in more detail with reference to Examples below.

In the Examples and Comparative Examples, the radio wave reflectance was measured as a microwave reflection coefficient based on the voltage standing wave ratio when a rectangular waveguide was used and the tip of the waveguide was short-circuited. Weather resistance tests were conducted using a Sunshine Carbon Weather Meter under the conditions of a black panel temperature of 83°C and a due cycle of 12 minutes/(60 minutes of irradiation).
The appearance of the surface after a period of time (adverse changes such as discoloration, fading, gloss, crazing, blistering, peeling of metal foil, cracking, etc.) was evaluated.

In addition, a heat cycle test was performed to heat the sample to 80°C for 2
After exposure for 4 hours, the sample was gradually cooled to -45°C, exposed to this temperature for 2 hours, and then gradually heated to 80°C over 4 hours, and after repeating this cycle 100 times. The surface appearance was evaluated in the same manner as in the weather resistance test. In addition, the bending rigidity was measured according to ASTM D-780, and the thermal expansion coefficient was determined according to ASTM D-898.
Measured according to.

The types and physical properties of the paints, olefin polymers, inorganic fillers, and metal foils used in the Examples and Comparative Examples to form the coating layer 11 are shown below.

[(A) Coating 4 As Coating 1, a two-component fluororesin (manufactured by Dainippon Toyo Co., Ltd.,
A two-component polyurethane resin (manufactured by Nihon Yushi Co., Ltd., trade name Hi-urethane, hereinafter referred to as "U paint") was used.

[(B) Olefin polymer As a coolefin polymer, a propylene-ethylene block copolymer with an MFI of 0.7 g 710 minutes (ethylene content 1015% by weight, hereinafter referred to as r P P j >, M , a high-density ethylene mass composite with an I of 20 g/10 min ('f: degree 0.981 g/cm
', hereinafter referred to as rHDPE') was used.

[(C inorganic filler) As an inorganic filler, talc with an average particle size of 3 microns (aspect ratio of about 7), mica with an average particle size of 3 microns (aspect ratio of 8), glass fiber (single fiber diameter 11 microns, cut length 3+nm, hereinafter r
GFJ) and calcium carbonate (hereinafter referred to as rcacO3J) having an average particle size of 0.8 microns were used.

[(D) Metal foil] Aluminum foil each having a thickness of about 20 microns (
Copper, brass and silver foil were used.

Examples 1 to 9, Comparative Examples 1.2 An epoxy resin primer (manufactured by Dainippon Toyo Co., Ltd., trade name: V-Fron Primer) was applied to one side of the metal foil whose type is shown in Table 1. It was coated to a thickness of 20 microns and dried.

Paints whose types are shown in Table 1 (U paint for Example 6, F paint for the others) were applied to the primer-coated surface of the obtained metal foil so that the dry thickness was 30 microns.
-Leave it alone day and night. A urethane primer (manufactured by Toyo Mohin Co., Ltd., trade name: Atcoat 335) was applied to the other side of the metal foil having the coating layer thus obtained, so that the dry thickness was 15 microns. Apply and dry. Furthermore, an inorganic filler and an olefin polymer (the types of each inorganic filler and olefin polymer and the content of the inorganic filler in the composition are shown in Table 1. In Comparative Example 2, the inorganic filler 5 each)
Tri-blending was carried out using a Henschel mixer for 1 minute, and each mixture was used to produce a composition using a vented extruder at a resin temperature of 230°C. Each of the obtained compositions (pellets) was used to produce a sheet with a thickness of 2111 va using a T-Guy molding machine.A metal foil having a coating layer on one side of which the primer thus produced was applied; A sheet of olefinic polymer containing an inorganic filler was placed on a press plate (surface temperature 230°C) as shown in FIG.
Then, heat and pressure bonding was carried out for 5 minutes at a pressure of 100 kg/cm' (gauge pressure). In addition, in Fig. 1, A is #5
It is a film layer, and B is a metal layer (metal foil). Further, C is a sheet of an olefin polymer containing an inorganic filler (an inorganic filler-containing olefin polymer layer). moreover,
D is the press plate of the press machine. Furthermore, 1 is an epoxy resin-based primer coating, and 2 is a urethane-based primer coating.

The flexural modulus and thermal expansion coefficient of an olefin polymer sheet containing an inorganic filler were measured.

The results obtained are shown in Table 1.

(Hereinafter, blank spaces) The radio wave reflectance of each of the laminates obtained as described above was measured and found to be 88%. Furthermore, we conducted a weather resistance test and a heat cycle test, but no harmful changes such as discoloration, fading, change in gloss, crazing, blistering, peeling of metal foil, or cracks were observed on the surface of all samples except for Comparative Example 1. . However, in Comparative Example 1, the aluminum foil on the surface corroded.

[Brief explanation of the drawing]

FIG. 1 is a partially enlarged cross-sectional view showing the state of lamination when manufacturing each laminate in each example and comparative example. In Figure 1, A is a coating layer (however,
(not used in Comparative Example 1), B is a metal foil (metal layer) coated on both sides with each primer. Further, C is an inorganic filler-containing olefin polymer layer (an olefin polymer sheet containing an inorganic filler; however, Comparative Example 2 did not contain an inorganic filler). Furthermore, 1 is an epoxy primer coating (however, it was not used in Comparative Example 1), and 2 is a urethane primer coating. Patent applicant Showa Denko Co., Ltd. Representative Patent attorney Sei Kikuchi

Claims (1)

[Scope of Claims] A laminate comprising at least (A) a metal layer having a coating layer with good weather resistance and (B) an olefinic polymer layer containing an inorganic filler, wherein the coating layer is The thickness is between 5 microns and 1 mm, and the thickness of the metal layer is between 5 microns and 1 mm.
A laminate with good weather resistance, characterized in that the content of the inorganic filler is 10 to 80% by weight.