Layered composite material with decorative layer made from chromed metal

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention has a substrate obtained from a thermoplastic polymer, an intermediate layer provided on the substrate, and a decorative layer applied on the intermediate layer, and the decorative layer is a composite material composed of a chromiumized metal. Regarding laminates. Further, the present invention relates to a method for producing this composite material laminate, and the use of the composite material laminate as a reflective member or an insulating member of a molded product in the household equipment, furniture or electrical industry, construction industry, automobile industry or health field. Regarding the law.

【0002】

[Conventional technology]

Known composite laminates are particularly used in the furniture and household equipment industries, with substrate layers made primarily of wood or wood fibers, or of multiple sheets of paper press-molded with the addition of resin. On the other hand, it has a decorative layer applied by heat and pressure, and another thermosetting layer known as an overlay. The decorative layer in this case often has a wood grain, metallic luster or marble pattern. The decorative layer is often a laminate with a thermosetting layer.

【0003】

The disadvantage of such composite laminates is that these materials are somewhat susceptible to the moisture that penetrates from the edge of the material towards the central layer, making wood, wood fibers, and multiple sheets of paper moist. It is prone to swelling when exposed to minutes. Moreover, this type of composite laminate is difficult to mold.

【0004】

For a wide range of industrial applications in the automotive or electrical industry, there is a need for surface materials that have compressive strength, relatively high heat resistance, are easily manufactured, and are decorative.

【0005】

Surface materials that have long been used in the manufacture of furniture have two to three layers, such as a substrate layer, a decorative layer, and a thermosetting layer provided on top of the substrate layer. These layers are made into a composite material having a decorative layer by other bonding layers obtained from paper, an adhesive film or the like. However, such composite laminates are very complex to produce, often have high formamide content, and exhibit undesired swelling behavior.

【0006】

Another inconvenience of the composite material laminate is that each layer is relatively thin and susceptible to mechanical stress, and once each layer is bonded as a laminate, other components cannot be strengthened. Is.

【0007】

German Patent Application Publication No. 1722339 discloses a composite material laminate including a polypropylene substrate layer, a decorative layer arranged on the substrate layer, and a thermosetting layer applied on the decorative layer. In addition, German Patent Application Publication No. 19858173 describes a substrate layer of various other thermoplastic polymers, such as certain styrene copolymers or polyoxymethylene or polybutylene terephthalates, and decorations provided on them. A composite laminate consisting of a thermosetting layer on a layer and a decorative layer is described. The composite material laminate containing a substrate layer made of a thermoplastic polymer, for example, has increased heat resistance and moisture resistance as compared with a conventional composite material laminate having a substrate layer made of wood, wood fiber or paper material. It has the features of improved mechanical strength and ease of processing. However, the degree of rigidity and brittleness of each of the above polymer layers can be determined by processing and molding composite material laminates known from German Patent Application Publication No. 2722339 and German Patent Application Publication No. 19858173, especially in the field of automobiles. It indicates that there is an inconvenience in three-dimensional molding when manufacturing a member in the field of household products or the field of electrical products. Further, in such a composite material laminate, defects are often found in downstream operations such as surface coating or attachment of other functional parts.

【0008】

In some industrial applications, such as household appliances, or molded bodies in the electrical, construction, or automotive industries, the composite material laminates as described above act as insulating members or radiant heat or radiant ray reflecting members, and machines. It is important that it is more recyclable and that the functional parts can be easily integrated so that it can withstand thermal stresses, has excellent aging resistance and good adhesion to other materials. is there.

【0009】

[Problems to be Solved by the Invention]

The present invention has been made in view of the above circumstances, the purpose of which is to overcome the above-mentioned inconveniences, to be mechanically and thermally stable, to have aging resistance, and to be easily combined with other functional members. Further an object of the present invention is to provide an improved composite material laminate that acts as an insulating member or a radiant heat or radiant ray reflecting member.

【0010】

[Means for solving problems]

The above object of the present invention has a substrate obtained from a thermoplastic polymer, an intermediate layer provided on the substrate, and a decorative layer applied on the intermediate layer, and the decorative layer is composed of a chromiumized metal. It has been found by the present inventors that the solution is solved by the development of a composite material laminate.

【0011】

BEST MODE FOR CARRYING OUT THE INVENTION

In one embodiment, the composite laminate of the present invention may have a thermosetting layer on the decorative layer. In the new composite material laminate, a sandwich structure centered on a substrate having an intermediate layer on both sides of a substrate layer made of a thermoplastic polymer, a decorative layer on the intermediate layer, and optionally a thermosetting layer on the decorative layer. It is also possible to manufacture.

【0012】

The substrate material of the present invention is a reinforcing filler of 1 to 60% by mass, preferably 5 to 50% by mass, particularly preferably 10 to 40% by mass, based on the total weight of the substrate, for example, barium sulfate, magnesium hydroxide, and the like. Includes talc with an average particle size of 0.1-10 μm as measured by DIN66115, wood, flux, cauldron, glass fiber, coated glass fiber, long and short glass fibers, glass beads or mixtures thereof. The substrate material may further contain conventional additives such as light stabilizers, UV stabilizers, heat stabilizers, pigments, carbon blacks, lubricants, flame retardants, foaming agents and the like in acceptable amounts.

【0013】

Examples of thermoplastic polymers that make up the substrate are polypropylene, polyethylene, polyvinyl chloride, polysulfone, polyethylketone, polyester, polycycloolefin, polyacrylate, and polymethacrylate, polyamide, polycarbonate, polyurethane, polyacetal. For example, polyoxymethylene, polybutylene terephthalate, and polystyrene. In the present invention, both homopolymers and copolymers of these thermoplastic polymers can be used. In addition to the reinforcing filler, the substrate layer used in the present invention includes polypropylene, polyoxymethylene, polybutylene terephthalate or polystyrene, especially styrene, and a smaller amount of one or more comonomer, such as butadiene, α-methylstyrene. , Acrylonitrile, a copolymer of vinylcarbazole, or an ester of acrylic acid, methacrylic acid or itaconic acid. The new composite laminate may contain recycled materials of these thermoplastic polymers.

【0014】

In the present invention, polyoxymethylene may be a homopolymer, but may also be a copolymer with an aldehyde, for example formaldehyde, or a cyclic acetal. They have repeated carbon-oxygen bonds in the molecule and have a melt flow rate (MFR) of 5 to 50 g / 10 min, especially 5 to 30 g / 10 min, at 230 ° C and a load of 2.16 kg. is there.

【0015】

The styrene copolymer preferably contains acrylonitrile as a comonomer in an amount of 45% by mass or less, particularly 20% by mass or less. The melt flow rate (MFR) of a copolymer (SAN) composed of styrene and acrylonitrile at 230 ° C and a load of 2.16 kg according to ISO1133 is 1 to 25 g / 10 minutes, especially 4 to 20 g / 10 minutes. is there.

【0016】

It is preferable to use a copolymer composed of styrene, acrylonitrile of 35% by mass or less, particularly 20% by mass or less, and butadiene of 35% by mass or less, particularly 30% by mass or less. The melt flow rate of the above-mentioned copolymer composed of styrene, acrylonitrile and butadiene (ABS) at 230 ° C. and a load of 2.16 kg according to ISO1133 is 1 to 40 g / 10 minutes, especially 2 to 30 g / 10 minutes. is there.

【0017】

Other materials used for the substrate are especially polyolefins such as polyethylene or polypropylene, preferably polypropylene. In the present invention, polypropylene means a homopolymer or copolymer of propylene. Propylene copolymers are smaller amounts of propylene copolymerizable monomers, such as C.₂-C₈-1-Alkenes include, for example, ethylene, 1-butene, 1-pentene or 1-hexene. It is also possible to use two or more other comonomer.

【0018】

Examples of particularly suitable substrate materials are propylene homopolymers or copolymers of propylene with other copolymerizable 1-alkenes of 50% by weight or less and 8 or less carbon atoms. The propylene copolymer may be either a random copolymer, a block copolymer or an impact-resistant copolymer. When the propylene copolymer has a random structure, it contains 15% by weight or less, preferably 6% by weight or less, and other 1-alkenes having 8 or less carbon atoms, such as ethylene, 1-butene or ethylene and 1-butene. Is common.

【0019】

Block copolymers or impact-resistant copolymers of propylene may be the propylene homopolymer or propylene in the first step and other 1- of up to 15% by weight, preferably 6% by weight, with 8 or less carbon atoms. A random copolymer with alkene is produced, and a propylene-ethylene copolymer having an ethylene content of 15 to 80% by mass is polymerized with respect to this in the second step. This propylene-ethylene copolymer is another C₄-C₈-1-Alkenes may be included. The amount of the propylene-ethylene copolymer used in the copolymerization in this case is usually adjusted so that the proportion of the copolymer produced in the second step in the final product is 3 to 60% by mass.

【0020】

A Ziegler-Natta catalyst system can be used for polymerization for polypropylene production. This catalyst system contains, in particular, a co-catalyst in the form of an organoaluminum compound b) and an electron donor compound c) in addition to the titanium-containing solid component a).

【0021】

However, it is also possible to use a catalyst system using a metallocene compound and a catalyst system having a metal complex, which are active in polymerization.

【0022】

In particular, a general Ziegler-Natta catalyst system uses a titanium-containing solid component, particularly a halide or alcoholate of trivalent or tetravalent titanium, and an inorganic oxide such as a halogen-containing magnesium compound or silica gel as a carrier, and further an electron donating compound. Is included. These are, for example, carboxylic acid derivatives or ketones, ethers, alcohols or organic silane compounds.

【0023】

The titanium-containing solid component is produced by a known method. Such manufacturing methods include, for example, European Patent Application Publication No. 45975, European Patent Application Publication No. 45977, European Patent Application Publication No. 171200, British Patent Application Publication No. 211066, US Patent No. 4857613, US Patent No. 4857613. It is described in each specification of No. 5288824. A method known from German Patent Application Publication No. 19592240 is preferably used.

【0024】

Examples of suitable aluminum compounds b) are, in addition to trialkylaluminum compounds, compounds in which the alkyl group in this compound is replaced by an alkoxy group or a halogen atom, such as chlorine or bromine. The alkyl groups in this compound may be the same or different from each other, and may be linear or branched. Trialkylaluminum having 1 to 8 carbon atoms in each alkyl group, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum or methyldiethylaluminum, or a mixture thereof is preferably used.

【0025】

Cocatalysts used in addition to aluminum compound b) are generally electron donating compounds c), such as monobasic or polybasic carboxylic acids, anhydrous carboxylic acids, carboxylic acid esters, or ketones, ethers, alcohols or lactones. It is an organic phosphorus or an organic silicon compound. The electron donating compound c) may be the same as or different from the electron donating compound used to produce the titanium-containing solid component a).

【0026】

It is also possible to produce polypropylene using a metallocene compound or a metal complex active in polymerization instead of the Ziegler-Natta catalyst system.

【0027】

In the present invention, metallocene is a complex composed of a transition group metal in the periodic table and an organic ligand, and becomes an effective catalytic system when used in combination with a metallocene ion-forming compound. When used for polypropylene production, this metallocene complex is often supported on a carrier in the catalyst system. Although the substrate often used is an inorganic oxide, an organic substrate made of a polymer such as polyolefin may be used. It is also preferable to use the above-mentioned inorganic oxide used for producing the titanium-containing solid component a).

【0028】

The central atom of the metallocene is usually titanium, zirconium, hafnium, preferably zirconium. The central atom is usually attached to at least one normally substituted cyclopentadienyl group by a π bond and to yet another substituent. Examples of other substituents are halogen, hydrogen or organic radicals, preferably fluorine, chlorine, bromine or iodine, or C.₁-C₁₀It is alkyl. The cyclopentadienyl group may be a component of a suitable heteroaromatic composition.

【0029】

Metallocenes in which the central atom is attached to two substituted cyclopentadienyl groups via two identical or different π bonds are preferably used. Of these, particularly suitable metallocenes are those in which each substituent of the cyclopentadienyl group bonded to both cyclopentadienyl groups is present. Particularly preferred is a complex in which the substituted or unsubstituted cyclopentadienyl group is further substituted on two carbon atoms adjacent to the cyclic group, and these cyclic groups may be integrated in a heteroaromatic system. Used.

【0030】

Another preferred metallocene is a metallocene that contains one substituted or unsubstituted cyclopentadienyl group but is substituted with at least one radical that is also attached to the central atom.

【0031】

Examples of suitable metallocene compounds are shown below. Ethylenebis (indenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) zirconium dichloride, diphenylmethylene-9-fluorenylcyclopentadienyl zirconium dichloride, dimethylsilanediylbis (3-tert-butyl-5-methylcyclopentadi) Enyl) zirconium dichloride, dimethylsilanediyl-(2-methyl-4-azapentalene)-(2-methyl-4- (4'-methylphenyl) indenyl) zirconium dichloride, dimethylsilanediyl-(2-methyl-4-thiapentalene) )-(2-Ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride, ethanediyl-(2-ethyl-4-azapentalene)-(2-ethyl-4- (4'-tert-butylphenyl)-(2-ethyl-4- (4'-tert-butylphenyl) ) Indenyl) Zyroxide dichloride, dimethylsilanediylbis (2-methyl-4-azapentalene) zirconium dichloride, dimethylsilanediylbis (2-methyl-4-thiapentalene) zirconium dichloride, dimethylsilanediylbis (2-methylindenyl) zirconium Dichloride, dimethylsilane diylbis (2-methylbenzindenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-4-naphthylindenyl) Zylzyl dichloride, dimethylsilane diylbis (2-methyl-4-isopropylindenyl) zirconium dichloride, and dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, as well as the corresponding dimethylzirconium.

【0032】

These metallocene compounds may be produced by using known substances as they are or by known methods. Further, a mixture of such metallocene compounds may be used for catalysis, or the metallocene complex described in US Pat. No. 416815 may be used.

【0033】

The metallocene catalyst system further comprises a metallocene ion-forming compound. Suitable examples are strong Lewis acids, neutral Lewis acids, ionic compounds with Lewis acid cations, and ionic compounds with Bronsted acid as cations. Examples of these are tris (pentafluorophenyl) borane, tetrakis (pentafluorophenyl) borate, and salts of N, N-dimethylanilinium. Other suitable metalrosenium ion forming compounds are linear or cyclic aluminoxane compounds. These are usually produced by reacting a trialkylaluminum compound with water and are obtained as a mixture of linear and cyclic molecules of various lengths.

【0034】

Furthermore, the metallocene catalyst system can be prepared by using organometallic compounds of the first, second and third main metals in the periodic table, such as n-butyllithium, n-butyl-n-octylmagnesium, triisobutylaluminum, triethylaluminium or trimethylaluminum. It may be included.

【0035】

Polypropylene used as a substrate layer is also produced by polymerization in at least one reaction zone, but is generally gas phase, suspended in two or more reaction zones arranged in series (reactor cascade). It is often produced by polymerization in a liquid or liquid phase (lump). C₂-C₈-1-A conventional reactor used for the polymerization of alkenes is used. Examples of suitable reactors are continuous stirring reactors, loop reactors, fluidized bed reactors. The size of the reactor is not important here, but is determined by the amount of processing in each reaction band.

【0036】

A fluidized bed reactor or a horizontal or vertical stirring powder bed reactor is particularly preferably used. This reaction bed generally polymerizes in each reactor C₂-C₈-1-Consists of a polymer obtained from an alkene.

【0037】

Polypropylene used as the substrate layer is produced by polymerization at 40 to 120 ° C, especially 50 to 100 ° C, under normal reaction conditions under pressure of 10 to 100 bar, especially 20 to 50 bar.

【0038】

The melt flow rate (MFR) of polypropylene used as a substrate according to ISO 1133 at 230 ° C. and a load of 2.16 kg is 0.1 to 200 g / 10 minutes, especially 0.2 to 100 g / 10 minutes.

【0039】

As the substrate of the novel composite material laminate, a blend, i.e. a mixture of various thermoplastic polymers, may be used, for example, a blend containing a copolymer of styrene and acrylonitrile and a combination of butadiene and acrylonitrile. Examples include blends containing polymers.

【0040】

The novel composite laminate of the present invention includes an intermediate layer on the substrate. The intermediate layer and the substrate are preferably made of the same thermoplastic, which greatly improves the adhesiveness between the substrate and the intermediate layer. The intermediate layer is particularly preferably a thin film or thin web with a thickness of 0.001 to 1.0 mm, particularly 0.005 to 0.3 mm. The material used for the intermediate layer is the thermoplastics mentioned above for substrates, in particular polypropylene, polyethylene, styrene polymers, polyoxymethylene, or polybutylene terephthalate.

【0041】

Other materials preferably used as the intermediate layer are resin-penetrated webs and resin-penetrated thermoplastic films. Preferred examples of the resin used here are an acrylate resin, a phenol resin, a urea resin, or a melamine resin. The degree of resin treatment can be 300% or less, that is, practically the entire surface of the intermediate layer can have one or more resin coatings. The degree of resin coating is preferably 50 to 150%, particularly preferably 80 to 120%. Middle layer m²The mass per unit is 15 to 150 g, especially 30 to 60 g.

【0042】

The composite material laminate of the present invention further has a chromiumized metal as a decorative layer. The position of the chromium metal is set to the upper part of the intermediate layer, and the decorative layer is set to 0.1 to 0.5 mm, preferably 0.1 to 2.0 mm, particularly preferably 0.1 to 1.0 mm. Even if the chromiumized metal used here is a layer made of chromium, a layer of another metal such as stainless steel, iron, copper, nickel, tin or zinc, or an appropriate alloy of these metals is provided, and this layer is provided. May be further coated with a chrome layer. As the chromiumized metal used in the present invention, it is also possible to use a layer obtained by coating a suitable thermoplastic polymer layer with a chromium layer as another layer. Examples of thermoplastic polymers suitable in this case are polyolefins such as polypropylene or polyethylene, polyamides, polycarbonates, and styrene copolymers such as SAN or ABS.

【0043】

The structure of the decorative layer obtained from the chromiumized metal has both reflective and insulating properties. The decorative layer of the present invention has a surface as smooth as possible so as to reflect radiation rays well. In order to impart good insulating properties to the composite material laminate of the present invention, it is desirable to make the decorative layer very thick, and further provide a very thick thermosetting layer (overlay). .. This overlay is usually composed of a thermosetting resin and acts as a good insulating material. Since this laminated structure avoids thermal and mechanical damage to the thermoplastic substrate, the composite laminate of the present invention does not tend to soften even at relatively high temperatures.

【0044】

The composite laminate may further include a thermosetting layer on top of the decorative layer described above.

【0045】

The thermosetting layer (overlay) arranged on the decorative layer is obtained by cross-linking a paper material impregnated with, for example, acrylic resin, phenol resin, melamine resin or urea resin by pressurization and heating during the production of a composite material laminate. It is preferably composed of a thermosetting material. The mass of the thermosetting layer (overlay) is usually 10 to 300 g / m.², Preferably 15 ~ 150g / m², Especially preferably 20 ~ 70g / m²Is.

【0046】

It is also possible to pre-install a thermosetting layer (overlay) and a decorative layer on one or both sides of the intermediate layer to form a directly usable laminate. This type of directly usable laminate is known, and it is also possible to use a commercially available product manufactured by Melaplast of Schweinfurt, Germany.

【0047】

In the production of a new composite material laminate, each material of the intermediate layer, the decorative layer, and the thermosetting layer when the thermosetting layer is used is made into a thin sheet, and these are combined with the material for the substrate layer at 150 to 300 ° C. It is preferably carried out by a manufacturing method by heating at 160 to 280 ° C. It is also preferred to use the intermediate layer, decorative layer and thermosetting layer (overlay) as a single sheet, directly usable laminate.

【0048】

Further, in the present invention, the intermediate layer, the decorative layer, and the thermosetting layer (if used) are bonded by immersion in an adhesive bath or press working with a thin adhesive piece, especially double belt press working, and then It is also possible to apply the obtained composite to a substrate. In this case, the composite obtained from the intermediate layer, the decorative layer, and optionally the thermosetting layer is two-dimensionally molded by thermoforming or direct molding, for example, injection molding, and then this is a thermoplastic resin to be a substrate. It is also effective to integrate with and by coating, extrusion or thermoforming in the mold. When the substrate and the intermediate layer are made of the same thermoplastic resin, the adhesiveness between the two layers becomes very strong.

【0049】

According to another embodiment of the method for producing a new composite laminate, after the composite laminate has been heat treated at 150-300 ° C, preferably 150-250 ° C, particularly preferably 160-200 ° C. , Three-dimensional molding is performed. This method is used for the production of articles, especially in the electrical, construction and automotive industries.

【0050】

Another method of producing new composite laminates is to use conventional treatment methods in the plastics industry for joining intermediate layers, decorative layers, thermosetting layers (if used), and substrates. Examples of this conventional method are injection molding, extrusion, and hot pressure molding of each layer.

【0051】

In injection molding, each of the above layers, i.e., a substrate, an intermediate layer, a decorative layer, and optionally a thermosetting layer (each of these layers can be in the form of a laminate that can be used directly as described above). ), Direct pre-molding by thermoforming and then inner-coating each other in an injection-molded mold, or directly molding by injection-molding to inner-coat the mold. This operation is performed on one or both sides of the substrate, and when this operation is performed on both sides, an intermediate layer, a decorative layer, and optionally a thermosetting layer are arranged on both sides of the substrate. This injection molding operation is performed at a temperature of 150 to 300 ° C, preferably 180 to 280 ° C, particularly preferably 190 to 270 ° C, 50 to 100 N / cm.², Especially 60 ~ 80N / cm²It is done under the pressure of. The temperature and pressure in this injection molding not only provides very good adhesion of the thermoplastic intermediate layer to the thermoplastic substrate, but also allows the new composite laminate to be further cured. Compared to known composite material laminates, the laminates of the present invention are extremely flexible and can be molded well in downstream processing steps.

【0052】

In the extrusion molding method, the intermediate layer, decorative layer and thermosetting layer of the composite material laminate of the present invention are fed to one side or both sides of the thermoplastic as a substrate by a temperature control calendar roll or an embossing roll (this). The method is known as a laminating method), and they are coupled to each other. Set the temperature to 150-300 ° C, preferably 160-250 ° C, particularly preferably 170-220 ° C, and set the pressure to 40-200 N / cm.², Preferably 50 ~ 100N / cm²Is usually the case. This results in very good adhesion between the layers. The obtained composite material laminate also has good surface properties.

【0053】

One form of extrusion molding is known as profile extrusion. In this method, each layer of the composite laminate of the present invention, especially the intermediate layer, is molded by a diameter measuring instrument, and the resulting layer is fed directly onto an actual deformed material, that is, a substrate made of thermoplastic plastic. Will be done.

【0054】

It is also possible to obtain a composite material laminate by hot-press molding each layer. Each layer may be preformed by an upstream thermoforming method or may be manufactured during pressing. This molding feeds thermoplastic pellets directly onto a composite laminate consisting of an intermediate layer, a decorative layer and (if used) a thermosetting layer, and the combination of these layers is 150-300 ° C. , Preferably 160-250 ° C, particularly preferably 170-230 ° C, and 50-120 N / cm.², Especially 80 ~ 100N / cm²It is carried out by press molding at a pressure of 0.5 to 10 minutes, preferably 1 to 5 minutes, particularly preferably 1 to 3 minutes.

【0055】

The composite material laminate of the present invention has good mechanical properties due to the good adhesiveness between the layers. Composite laminates are easily two-dimensionally or three-dimensionally molded, have excellent resistance to high temperatures and chemicals, and are also aging resistant. The new composite laminate is easily coupled to other functional devices and also has excellent insulation and reflection properties against radiant heat and / or radiant radiation. Another notable advantage of these materials is that such a laminate structure provides fracture resistance, which is very significant compared to conventional reflective members such as mirrors.

【0056】

The composite laminate of the present invention is suitable as a reflective or insulating member used in household appliances, furniture parts, electrical industry, construction industry, automobile industry, or health field.

【0057】

It is particularly important that the novel manufacturing method of the composite material laminate of the present invention is easily carried out and the conventional manufacturing and assembling method can be used.

【0058】

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, the following experiments were performed on the sample.

【0059】

-The gloss was visually evaluated. Impact strength was measured by a drop impact test from 1.75 m. -The flexural modulus at + 23 ° C, + 60 ° C, and + 90 ° C was measured according to ISO178. -Charpy impact strength at + 23 ° C and -20 ° C was measured according to ISO179 / 1eU. The heating deflection temperature was measured according to ISO75 / 1 + 2.

【0060】

[Example]

[Example 1 and Comparative Example A] The reflection characteristics of the novel composite material laminate (Example 1) and the conventional mirror (Comparative Example A) were compared.

【0061】

Composite laminate at 230 ° C, 2.16 kg, ISO 1133 meltle flow rate (MFR), substrate layer obtained from 15 g / 10 min propylene homopolymer, synthetic weight made of the same propylene homopolymer A composite laminate with an intermediate layer of coalesced non-woven fabric, a 0.2 mm thick chrome stainless steel decorative layer, and a 0.1 mm thick melamine resin overlay was used. The total thickness of this composite laminate was 1.4 mm, 90% of which was the thickness of the substrate.

【0062】

The gloss, reflection, and crushing behaviors of the composite material laminate of the present invention and a conventional mirror were compared. The measurement results are shown in Table I below.

【0063】

[table 1]

<img file="JP2001334603A_D0001.tif" />【0064】

From the results in Table I, it can be seen that, in particular, the composite material laminate of the present invention exhibits excellent crushing behavior while maintaining good gloss.

【0065】

[Example 2 and Comparative Example B] The mechanical stability and thermal stability of the composite material laminate of the present invention (Example 2) and a conventional test piece made of propylene (Comparative Example B) were compared.

【0066】

The composite material laminate of Example 2 is composed of the same intermediate layer, the same decorative layer, and the same overlay as the laminate of Example 1, but the thickness of the decorative layer of this example is It was 0.2 mm and the overlay thickness was 0.1 mm. The overall thickness of the composite laminate was 1.4 mm, 90% of which was the thickness of the substrate.

【0067】

The test piece of Comparative Example B was composed of a propylene homopolymer having a melt flow rate (MFR) of 15 g / 10 minutes at 230 ° C., 2.16 kg, and ISO1133.

【0068】

The dimensions of the composite material laminate of the present invention and the test piece of Comparative Example B were the same. These flexural modulus, Charpy impact strength, and heating deflection temperature (HDT / A) were measured. The measurement results are shown in Table II below.

【0069】

[Table 2]

<img file="JP2001334603A_D0002.tif" />【0070】

The results in Table II show particularly good flexural modulus, Charpy impact strength, and heat deflection temperature (HDT / A) for the composite laminates of the present invention.

【0071】

Embodiments of the composite material laminate of the present invention will be described in more detail below with reference to the drawings (FIGS. 1 to 5).

【0072】

[Explanation of FIG. 1] A metallocene catalyst was used to synthesize a toaster cover substrate (1) made of a propylene homopolymer having a melt flow rate (MFR) of 15 g / min at 230 ° C., 2.16 kg, and ISO1133. A laminate (2) consisting of a non-woven intermediate layer made of polypropylene and a decorative layer made of chrominated metal was applied. This lamination is to prevent the heat generated from the toaster device (4) from reaching the toaster cover substrate (1). For reasons of deformation, another suitable laminate (3) having the same configuration as the above laminate (2) was applied so as to face in a different direction from the above laminate (2). As a result, the space between the toaster device (4) and the toaster cover substrate (1) is reduced, and it is also used for a newly designed toaster.

【0073】

[Explanation of Fig. 2] An opening for a light emitting diode (3) is provided in the casing (1) of an electric toothbrush made of a propylene homopolymer having a melt flow rate (MFR) of 50 g / min according to 230 ° C, 2.16 kg, and ISO1133. Provided. A laminating layer (2) was provided around the opening provided in the casing to make the casing (1) around the light emitting diode (3) light-resistant, so that the light emitting diode could not be seen from the entire casing. The laminate layer (2) is composed of a decorative layer made of a chromiumized metal and a polypropylene non-woven intermediate layer synthesized by using a metallocene catalyst. The casing (1) in this case is a substrate for the laminate (2). The size and thickness of the laminate were set to be appropriate for the light output of the light emitting diode.

【0074】

[Explanation of Fig. 3] The substrate of the mirror (1) was obtained from a propylene copolymer in which 20% by mass of ethylene was introduced into propylene at 230 ° C., 2.16 kg, and a melt flow rate of 15 g / 10 minutes according to ISO1133. It was. A cover (4) is formed from the substrate (1) via a film hinge (5), and this cover covers and closes the reflective metal surface (2) of the laminate to prevent damage to the metal surface. To. The cover (4) is fixed to the substrate (1) by a hook (6) having a snapping action to prevent accidental opening. On the opposite surface of the substrate, a balance layer (3) having the same dimensions and the same configuration as the laminate layer having the reflective metal surface (2) is provided. This laminate layer is composed of an overlay made of a melamine resin, a decorative layer made of a chromiumized metal, and an intermediate layer made of a polypropylene non-woven fabric synthesized using a metallocene catalyst.

【0075】

[Explanation of Fig. 4] The illustrated casing of the lamp was obtained by applying 20% by mass of talc strengthening agent to a propylene homopolymer having a melt flow index of 15 g / 10 minutes at 230 ° C., 2.16 kg, and ISO1133. It was obtained by laminating a substrate and a reflective metal surface (2, 3) provided on the substrate. In this case, the front side was finished with another part of the laminate (3). The laminate used here is shown in FIG. The lamp (4) was placed between the two reflective laminated surfaces (2, 3) in the casing (1), and the light was reflected by the laminated surfaces (2) and (3). Fasteners for assembling the lamp (4) were also molded on the substrate (1).

【0076】

[Explanation of Fig. 5] Melt flowlet (MFR) at 230 ° C, 2.16 kg, ISO 1133, which is obtained by synthesizing the substrate (1) of the insulating laminate layer (2, 3) using a metallocene catalyst, is 50 g / min. Produced from a propylene homopolymer. The laminate used here is as shown in FIG. The substrate (1) constitutes both the casting bottom and the casting cover, and the two portions are connected to each other via a film hinge (4). For best shielding effect, the final shape of each laminate for the bottom (2) and side (3) formed corners where the laminates overlap.

[Simple explanation of drawings]

[Figure 1]

It is a figure of the toaster cover manufactured from the composite material laminate of this invention.

[Figure 2]

FIG. 5 is a diagram of a "light resistant" casing of an electric toothbrush.

[Fig. 3]

It is a figure which shows the structure of the "breaking resistance" mirror.

[Fig. 4]

It is a figure which shows the structure of the lamp (light) / household equipment for sunlight / reflective member.

[Fig. 5]

It is a figure which shows the structure of the casing which is electromagnetically shielded.