JPS60116440A - Laminate having excellent weatherproofness - 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 a laminate having good weather resistance and having a metal layer as an intermediate layer. More specifically, it is a laminate in which at least (5) a thermoplastic resin layer with good weather resistance, (B) a metal layer, and (C) an olefinic polymer layer containing an inorganic filler are laminated in sequence, and the thermoplastic The thickness of the resin layer is 5 microns to 15 mm, the thickness of the metal layer is 25 microns to 1 mm, and the thickness of the inorganic filler-containing olefin polymer layer is 500 microns to 15 mm. This relates to a laminate with good weather resistance, characterized in that the content of the inorganic filler in this layer is 10 to 80% by weight, and the metal layer as an intermediate layer reflects radio waves. The object is to provide a reflective laminate.

[II] Background of the Invention Conventionally, metal plates or metal nets have been used as radio wave reflectors. 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 multiple coats are applied, 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 as a radio wave reflective layer, but the manufacturing method is complicated and radio wave It was very difficult to maintain the reflective layer at a constant thickness and without unevenness.

[■] Structure of the Invention Based on the above, the present inventors have attempted 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 of various searches, we found that at least (3) a thermoplastic resin layer with good weather resistance;
) A metal layer and (C) an inorganic filler-containing olefin polymer layer are laminated in sequence, and the thickness of the thermoplastic resin layer is 5.
The thickness of the metal layer is 5 microns to 1 micron, and the thickness of the inorganic filler-containing olefinic polymer layer is 500 microns to 15 microns. In addition, the laminate with good weather resistance, characterized in that the content of the inorganic filler in this layer is 10 to 80 weight φ, has not only good durability but also good radio wave reflection properties. [IV] Effects of the Invention The laminate of the present invention exhibits the following effects (characteristics) 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) Since the difference in linear expansion coefficient between the metal layer and the inorganic filler-containing olefin polymer layer is extremely small, separation between the layers will not occur even if subjected to heat cycles (repetitive cold and heat cycles) for a long period of time. Does not occur.

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

(4) The metal layer can be formed uniformly, and 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.

(6) The laminate has excellent mechanical strength (dissociation, 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 Thermoplastic Resin The thermoplastic resin used to manufacture the thermoplastic resin layer of the present invention is widely produced industrially and used in many fields. The manufacturing method and various physical properties are well known. Their molecular weight varies depending on the type, but generally ranges from 10,000 to 1,000,000. Typical thermoplastic resins are homopolymers of monomers having double bonds such as ethylene, propylene, vinylidene fluoride, vinyl chloride, and styrene; ), copolymers of styrene and acrylonitrile (As resin), resins whose main component is methyl methacrylate (MMA resin), butadiene homopolymer rubber, acrylonitrile-butadiene copolymer rubber (NBR)
, Styrene-Butadiene Co M Gocom (SBR),
Acrylic rubber, ethylene-propylene copolymer comb (EP
R), obtained by graft copolymerizing styrene alone or styrene with other vinyl compounds (e.g., acrylonitrile, methyl methacrylate) onto rubbers such as ethylene-propylene-diene ternary copolymer rubber (EPDM) and chlorinated polyethylene. Examples include graft copolymer resins, polyamide resins, polyester resins, polyphenylene ether resins, and polycarnate resins. Furthermore, even if these thermoplastic resins are modified by grafting an organic compound having at least one double bond (for example, unsaturated caldic acid or its anhydride), the processability is excellent. If so, you can use it as you like. Furthermore, in addition to the above-mentioned graft copolymer resin (6), compositions obtained by blending these thermoplastic resins with the above-mentioned rubber (the blending ratio of rubber is generally at most 40% by weight) can also be used. can. Among these thermoplastic resins, fluorine-containing resins such as polyvinylidene fluoride are preferred because of their excellent weather resistance. Furthermore, resins mainly composed of vinyl chloride, resins mainly composed of ethylene and/or propylene, and graft copolymer resins obtained by graft copolymerizing styrene alone or styrene and other vinyl compounds to rubber, etc. Even with thermoplastic resins, the weather resistance can be improved by adding ultraviolet absorbers, so these formulations can also be used with preference.

(B) Metal layer Furthermore, typical examples of metals that are raw materials for the metal layer in the present invention include simple metals 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 combinations include ethylene homopolymers, propylene homopolymers, ethylene and propylene (!: (D 77 Dumb or block copolymers, and ethylene and/or propylene with carbon numbers up to Examples include random or block copolymers with 12 other α-olefins (the copolymerization ratio of α-olefins is at most 20% by weight).The melt index of these olefin polymers (according to JIS K6760) Measured at a temperature of 190°C and a load of 2.16 kg, hereinafter referred to as "M, 1".
．． ) or melt flow index (JIS
Measured according to K-6758 at a temperature of 230°C and a load of 2.16 kg, and preferably has an IJ of 0.01 to 100 g7xo, with a range of 0.01 to 80 g. /10 minutes is suitable.

M, 1. If an olefinic polymer with an i or MFI of less than 0.001 g/l 0 minutes is used, not only will the resulting composition be poor, but it will also have poor melt cross-talk, which will be described later, resulting in a uniform composition. It becomes difficult to obtain the composition. On the other hand, 1
If an olefin polymer with a ratio exceeding 00/10 minutes is used, the melt cross-mixability and moldability are excellent, but the mechanical properties of the resulting molded product are poor. Also, low density (0,
90097cm ) or high density (0,980g/sub3
), ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and random or block copolymers of ethylene or propylene with other α-olefins are preferred.

These olefin polymers are obtained by using a catalyst system (so-called Ziegler catalyst) obtained from a transition metal compound and an organoaluminium compound, and by supporting a chromium compound (for example, chromium oxide) on a carrier (for example, silica). (9) Catalytic systems (so-called Phillips catalysts) or radical initiators (e.g. organic peroxides)? It can be obtained by homopolymerizing or copolymerizing olefins.

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

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

The production methods for these olefin polymers and modified polyolefins are well known.

(D) Inorganic filler and the inorganic filler-containing olefinic polymer layer (10) The inorganic filler used for the overall production 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 that do not decompose during crosstalk or molding. The inorganic fillers include metals such as aluminum, copper, iron, lead and nickel, oxides of these metals and metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony and titanium, and their water. It is broadly classified into compounds such as hydrates (hydroxides), sulfates, carbonates, silicates, their double salts, and mixtures thereof. Typical examples of the inorganic fillers include the metals mentioned above, aluminum oxide (alumina), its hydrates, calcium hydroxide, magnesium oxide (magnesia), magnesium hydroxide, zinc oxide (zinc flakes), red lead, and lead. White lead oxide, magnesium carbonate, calcium carbonate, chlorinated magnesium carbonate, white carbon, asbestos, mica, talc, glass fiber, glass powder, glass peas, clay, diatomaceous earth, silica, wollastonite, Examples include iron oxide, antimony oxide, titanium oxide (titania), lithopone, pumice powder, aluminum sulfate, calcium sulfate (gypsum, etc.), turconium silicate, zirconium oxide, barium carbonate, barium sulfate, dolomite, molybdenum disulfide and iron sand. . Among these inorganic fillers, those in powder form preferably have a diameter of 1 or less (preferably 0.5 or less). In addition, for fibrous materials, the diameter is 1~
500 microns (preferably 1-300 microns) and length 0.1-6. (preferably 01-5) is desirable. Furthermore, it is preferable that the diameter of the flat plate is 2 or less (preferably 1 or less).

(g)) Structure of each layer (1) Thermoplastic resin layer The thermoplastic resin layer of the present invention serves to prevent corrosion of the metal layer described later. From this, the thickness is preferably 5 microns to 5rrrm, preferably 10 microns to 15rr, particularly 10 microns to 1r.
rrm is preferred. If the thickness of this thermoplastic resin layer is less than 5 microns, not only corrosion of the metal layer will occur, but also
There is a problem in that the metal layer is exposed due to wear due to contact and friction with other articles during use. On the other hand, if it exceeds 5rIrJn, it is undesirable because it not only reduces the radio wave reflectance but also increases the cost and increases the weight of the laminate.

(2) Metal layer The metal layer of the present invention functions to reflect radio waves. The thickness of this metal layer is between 5 microns and 1 thick.
˜500 microns is preferred, with 10 to 500 microns particularly preferred. 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, resulting in problems in terms of appearance and performance. On the other hand, if it exceeds 1 yo, not only does the weight increase, but also the cost increases, and furthermore, it causes problems when bending or bending the laminate.

(13) (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., olefin polymer layer). The composition ratio of the combination is 90 to 20% by weight), 1
A weight ratio of 0 to 70 is preferable, and a weight ratio of 10 to 60 is particularly preferable.

If the composition ratio of the inorganic filler in the inorganic filler-containing olefin polymer layer is less than 10% by weight, 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 peeling may occur between the metal layer and the inorganic filler-containing olefin polymer layer due to cycling, and that the resulting laminate lacks rigidity. On the other hand, if it exceeds 80% by weight, it is difficult to produce a uniform composition, and even if a uniform composition is obtained, it is difficult to produce a laminate in sheet production or injection molding as described below. When manufacturing, it is not possible to obtain a good product (laminate).

The thickness (14) of this inorganic filler-containing olefinic polymer layer is from 500 microns to 15 microns, preferably from 1 to 10 microns, particularly preferably from 1 to 7 microns.

If the thickness of the inorganic filler-containing olefin polymer layer is less than 500 microns, the rigidity will be insufficient and T1 will be insufficient because it will be deformed and damaged by external force. On the other hand, if it exceeds 15 mm, it will take time to cool down during molding, and not only will sink marks easily occur on the surface, but the weight will increase, causing problems in use.

In producing the thermoplastic resin layer and the inorganic filler-containing olefin polymer layer, stabilizers against oxygen, heat and ultraviolet rays, metal deterioration inhibitors, flame retardants, and colorants commonly used in the respective fields are used. The compositions of the thermoplastic resin layer and the inorganic filler-containing olefinic polymer layer of the present invention contain additives such as, electrical property modifiers, antistatic agents, lubricants, processability modifiers, and tack modifiers. It may be added within a range that does not impair the properties.

A set of screws normally used in each industry when blending the above additives into the thermoplastic resin of the present invention and when producing an inorganic filler-containing olefin polymer (including when blending the above additives). It can be produced by melt-kneading using a mixer such as an extruder, Banbury mixer, kneader, or roll mill.

At this time, a more uniform composition (compound) can be produced by triblending in advance using a mixer such as a Henschel mixer and further melt-kneading the resulting mixture.

When melt-kneading is performed to produce the above blends, it must be carried out at a temperature higher than the melting point or softening point of the thermoplastic resin or olefinic polymer used, but if carried out at a high temperature, the thermoplastic resin and olefin polymer may The system polymer deteriorates. For these reasons, the temperature is generally 20°C higher than the melting point or softening point of the respective thermoplastic resin or olefin polymer (preferably, a temperature higher than 50°C), but the temperature does not cause deterioration. Implemented within a range.

(F) Manufacture of laminate The laminate obtained by the present invention consists of (5) a thermoplastic resin layer, (B) a metal layer and an inorganic filler-containing olefinic polymer layer as described above. 1 is a partially enlarged sectional view of a laminate according to the present invention, which is explained in more detail with reference to FIG. 1; FIG. In FIG. 1, 1 is a thermoplastic resin layer and 2 is a metal layer. Further, 3 is an olefin polymer layer containing an inorganic filler. The laminate of the present invention is composed of a thermoplastic resin layer, a metal layer, and an inorganic filler-containing olefin polymer layer. If they have good adhesion, they can be used as is, but if they have poor adhesion, use a primer or other adhesive agent to maintain sufficient adhesion (adhesion) between them. An agent may also be present.

There are various (17) methods for manufacturing the laminate of the present invention. Typical examples of this method include applying an adhesive agent to one side of the metal layer in advance and extrusion laminating the thermoplastic resin layer, or applying an adhesive to one side of the metal layer in advance and press-molding the thermoplastic resin layer. The obtained laminate may be laminated with an inorganic filler-containing olefin polymer layer as described below. At this time, if the adhesion between the thermoplastic resin layer and the metal layer is good, the laminate may be manufactured by directly extrusion laminating or press molding without applying an adhesive to the metal layer. In order to laminate the inorganic filler-containing olefin polymer layer on the laminate thus obtained, an adhesion imparting agent is applied in advance to the other surface of the metal layer to which the thermoplastic resin layer is in close contact. The inorganic filler-containing olefin polymer layer may be extrusion laminated or press molded. Furthermore, the laminate can also be manufactured by inserting the olefin polymer containing an inorganic filler into a mold of an injection molding machine in advance and injection molding it. If any of these methods has excellent adhesion between the metal layer and the inorganic filler-containing olefin polymer layer (18), these methods can be used without applying an adhesion promoter to the metal layer. A laminate may be manufactured by molding. In addition, a laminate is produced by manufacturing a metal layer and an inorganic filler-containing olefin polymer layer in advance by extrusion lamination, press molding, or insert injection molding with or without the intervention of an adhesion agent, and the resulting laminate An extrusion lamination method in which a thermoplastic resin layer is applied to the object with or without an adhesion agent,
They may be brought into close contact by a press molding method or a thermocompression bonding method. Furthermore, the thermoplastic resin layer, the metal layer, and the inorganic filler-containing olefin polymer layer are laminated in this order with or without intervening an adhesion agent between each layer, and manufactured by heat-pressing. You may. None of the extrusion lamination method, press molding method, insert injection molding method, and thermocompression bonding method described above is unique to the present invention, and commonly used methods 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 thermoplastic resin and inorganic filler-containing olefin polymer used do not undergo thermal deterioration. The methods for manufacturing these laminates are merely some examples, and other methods may be applied.

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

In the Examples and Comparative Examples, the radio wave reflectance was measured as a microwave reflection coefficient from the voltage standing wave ratio when a rectangular waveguide was used and the tip of the waveguide was short-circuited. The weather resistance test was conducted using a Sunshine Carbon Weather Meter, and the surface appearance (discoloration, fading, Deleterious changes such as changes in gloss, crazing, blistering, peeling of metal foil, and cracks) were evaluated.

Furthermore, the heat cycle test was performed by heating the sample to 80℃ for 2 days.
After being exposed for 4 hours, the sample was gradually cooled to -45℃ over 4 hours, exposed to this temperature for 2 hours, and then gradually heated to 80℃ 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.

Moreover, the bending rigidity was measured according to ASTM D-790, and the thermal expansion coefficient was measured according to ASTM D-696.

The types and physical properties of the thermoplastic resin, olefin polymer, inorganic filler, and metal foil used in the thermoplastic resin layer in Examples and Comparative Examples are shown below.

[(A) Thermoplastic resin]

As a thermoplastic resin, melt flow rate (ASTM
Polyvinylidene fluoride (hereinafter referred to as "PvdF") having a temperature of 6.1 j; 7710 minutes (measured according to D-1238 at a temperature of 250 °C and a load of 10 k17)
, a propylene homopolymer containing 0.4 parts by weight of a benzotriazole-based ultraviolet absorber and 0.5 parts by weight of carbon black [melt flow index (JIS
K-6758, measured at a temperature of 230°C and a load of 2.16 kg, hereinafter referred to as rMFIJ) was 0.5 g/10 minutes, hereinafter referred to as r pp (A)J], pen (21) High-density polyethylene containing 0.4 parts by weight of a citriazole-based ultraviolet absorber and 0.5 parts by weight of carbon black [density 0.958 g/cm3, melt index (temperature 190 according to JIS K-6760)]
Measured under the conditions of temperature and load of 2.16 kg, hereinafter referred to as "M
, I, j) is 0.8 g/10 minutes, hereinafter referred to as rH
20 parts by weight of chlorinated polyethylene (chlorine content 31.5 parts by weight, amorphous, molecular weight of raw material polyethylene approximately 200,000) having a Mooney viscosity (ML, +4) of 108 (referred to as DPE(1)J) and 80 parts by weight of an acrylonitrile-styrene copolymer resin (acrylonitrile content: 23% by weight) and 2 parts by weight of a dibutyl tin malate stabilizer [manufactured by Sankyoki Gosei Co., Ltd., trade name: Stann BMI]. Roll (surface temperature 1'8
The resulting composition (hereinafter referred to as "Ac1") was mixed with 20 parts by weight of dioctyl phthalate (as a plasticizer) and 5.0 parts by weight of dibutyltin malate (desalinated As a hydrogen inhibitor)'ii
l O0 parts by weight of vinyl chloride homopolymer (degree of polymerization 110
0, hereinafter referred to as "rpvc")22) was used.

[(B) Olefin polymer]

As an olefin polymer, a protlene-ethylene block copolymer (ethylene content 10.5% by weight, hereinafter referred to as "PP(B)") whose MP processing is 0.7 g/10 minutes is used.
,M,1. High-density ethylene homopolymer [density 0.961 g/cm, hereinafter referred to as rHDPE]
(2) j] was used.

[(C) Inorganic filler]

As an inorganic filler, talc with an average particle size of 3 microns (astegen coverage ratio of about 7) is used. Mica with an average particle size of 3 microns (astral coverage ratio of about 8), glass fiber (single fiber diameter 111 microns, cut length 3 mm, hereinafter referred to as rGF'j) and an average particle size of 0.8 microns. Calcium carbonate (hereinafter referred to as "CaCO3") was used.

[(D) Metal foil]

Aluminum (each approximately 20 microns thick)
(hereinafter referred to as "At"), copper, brass, and silver foils were used.

Examples 1-12. Comparative Examples 1 and 2 The thermoplastic resins were molded to produce films each having a thickness of 20 microns. First, apply an acrylic primer (manufactured by Showa Kobunshi Co., Ltd., trade name Vinyroll 92T) to one side of each metal foil to a thickness of microns, and apply urethane primer (manufactured by Toyo Morton Co., Ltd.,
Adko (trade name) 335) was applied to a thickness of microns and dried (Examples 8 and 9).
Then, apply the urethane primer on both sides) 0 Furthermore, inorganic filler and olefin polymer (types of each inorganic filler and olefin polymer and content of inorganic filler in the composition are shown in Table 1). In Comparative Example 2, each mixture (without inorganic filler) was triblended using a Henschel mixer for 5 minutes, and each mixture was mixed using a vented extruder at a resin temperature of 230°C. .

The thermoplastic resin film produced in this manner (not used in Comparative Example 1), the metal foil coated on both sides with a primer, and the sheet of olefinic polymer containing an inorganic filler are shown in Figure 1. As shown in the press plate (
The surface temperature was 230℃) and the pressure was 100kg/cm2 (r-
Heat and pressure bonding was carried out for S minutes at a pressure of In addition, in Figure 1,
1 is a heated olefin polymer sheet (an inorganic filler-containing olefin polymer layer), and 1.4 is a press plate of a pressure press machine. Furthermore, a is a coated product of an acrylic primer (however, Examples 8 and 9 are coated products of a urethane-based primer), and b is a coated product of a urethane-based primer.

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.

(25) When the radio wave reflectance of each of the laminates obtained as described above was measured, it was 98 in all cases.

Further, a weather resistance test and a heat cycle test were conducted, but no harmful changes such as discoloration, fading, change in gloss, crazing, blistering, peeling of metal foil, cracking, etc. were observed on the surface of all samples except Comparative Example 11c. However, in Comparative Example 1, the aluminum foil on the surface corroded.

[Brief explanation of drawings]

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 FIG. 1, 1 is a thermoplastic resin layer (thermoplastic resin film, however, not used in Comparative Example 1), and 2 is a metal foil coated on both sides with each primer. In addition, 3 is an inorganic filler-containing olefin polymer layer (
4 is a press plate. Furthermore, a is a coating of an acrylic primer (in Examples 8 and 9, a urethane primer), and b (27) is a coating of a urethane primer. Patent applicant Sei Kikuchi, patent attorney representing Showa Denko Co., Ltd. (28)

Claims (1)

[Scope of Claims] At least (A) a thermoplastic resin layer with good weather resistance;
) A laminate consisting of a metal foil and (C) an inorganic filler-containing olefin polymer layer that are successively laminated, the thermoplastic resin layer having a thickness of 5 microns to 5 microns, and the thickness of the metal layer is 5 microns to 1 inch, and the float of the inorganic filler-containing olefin polymer layer is 500 microns to 15 nm, and the content of the inorganic filler in this layer is 10 to 80% by weight. A laminate with good weather resistance.