JPH0197639A - Laminate - Google Patents

Abstract

PURPOSE:To obtain laminates of good adhesiveness, by modifying the resin of a contact layer with a specific unsaturated compound containing functional groups in lamination of a sheet compring a vinylidene fluoride resin layer and a thermoplastic resin layer with a molding such as of polyamide resin or rubber reinforced stylene resin. CONSTITUTION:A laminate (a) of a single layer of vinylidene fluoride resin a1 and a thermoplastic resin layer a2 is laminated on the surface of b layer consisting mainly of a composition of nylon and polyphenylene either resin or that of nylon and fibers. For improvement of adhesion with a layer contacting b layer, one of a multilayer is allowed to contain the component of an unsaturated compound (c) containing functional groups. This compound is an unsaturated compound containing a hydroxyl group and anhydride group. The method of modifying includes copolymerization of (c) component for polymerization of main components a1, a2; compounding the copolymer of a single polymer of (c) component and another vinyl monomer with another layer; and melt kneading the main component of another layer in the presence of (c) component.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention provides a vinylidene fluoride resin layer and a polyamide resin, a polyphenylene ether resin, a polycarbonate, a thermoplastic polyester resin, and a rubber-reinforced styrene resin. It relates to a laminate consisting of a small number of layers.

b. Conventional technology Polyamide resins, polyphenylene ether resins, polycarbonates, thermoplastic polyester resins, rubber-reinforced styrene resins, and mixtures thereof are called engineering plastics and are widely used because of their excellent properties. It is used as a material for industrial parts and vehicle parts that require functionality, as well as new products and various products that require durability.

A common drawback of polyamide resins, polyphenylene ether resins, polycarbonates, thermoplastic polyester resins, and rubber-reinforced styrene resins is that although they exhibit excellent chemical resistance to certain chemicals and solvents, It does not exhibit excellent chemical resistance to chemicals. In addition, it is well known that when used outdoors for a long time, cracks occur on the surface, which can cause breakage, discoloration, and the surface is easily soiled, making it difficult to remove the contaminated parts. There is.

Therefore, polyamide resins, polyphenylene ether resins, polycarbonate, thermoplastic polyester resins, and rubber-reinforced styrene resins are used in a limited range due to performance constraints for exterior applications. However, even in a limited range, they were used with unsatisfactory performance, and improvements in performance were desired, but rarely.

Recently, due to the need for higher performance, cost reduction, fashionability, and improved productivity of molded products, thermoplastic resin molded products made by various molding methods are being used as exterior parts that are used in harsh environmental conditions. is being considered, but
Lack of chemical resistance and weather resistance are major obstacles.

As a method for improving chemical resistance, it is widely known to improve chemical resistance by adding a resin having excellent chemical resistance.

Although this method can be expected to improve to some extent, it is still not sufficient, and the excellent properties of engineering plastics may be impaired.

As methods for improving weather resistance, for example, a method of adding an ultraviolet absorber, a method of adding a large amount of inorganic substances or pigments with excellent weather resistance, etc. have been proposed.

Although these methods are effective in the short term, their effects cannot be sustained over the long term.

In addition, a method of adding an antistatic agent has been proposed as a method to prevent staining. Although this method has some effect in the short term, the effect cannot be maintained for a long period of time. Furthermore, the addition of the above-mentioned additives may cause deterioration of the excellent properties of engineering plastics.

On the other hand, vinylidene fluoride resin has excellent molding fluidity, chemical resistance, weather resistance, heat resistance, non-adhesiveness, and ease of stain removal, but it is very expensive, and vinylidene fluoride resin Obtaining a molded product is cost-effective and has no versatility.

Therefore, one possible method to improve the chemical resistance and weather resistance of polyamide resins, polyphenylene ether resins, polycarbonates, thermoplastic polyester resins, and rubber-reinforced styrene resins is to laminate them with vinylidene fluoride resins. Due to its performance, vinylidene fluoride resin is used as a polyamide resin, polyphenylene ether resin,
It has poor fusion and adhesive properties with polycarbonate, thermoplastic polyester resins, rubber-reinforced styrene resins, etc., there is no suitable adhesive, and the number of bonding steps increases, resulting in poor productivity. It was not possible to hire him.

Problems to be solved by the C0 invention The inventors:
We conducted intensive studies to obtain a laminate with improved interlayer adhesion between the surface layer made of vinylidene fluoride resin and the layer made of polyamide resin, polyphenylene ether resin, polycarbonate, thermoplastic polyester resin, and rubber-reinforced styrene resin. As a result, molding of vinylidene fluoride resin sheets or sheets consisting of vinylidene fluoride resin layers and thermoplastic resin layers, polyamide resins, polyphenylene ether resins, polycarbonates, thermoplastic polyester resins, rubber-reinforced styrene resins, etc. We have discovered that a laminate with good adhesion can be obtained by modifying one or both of the resins in the contacting layer with a specific functional group-containing unsaturated compound when laminating the product with the product, and based on this knowledge, The present invention has now been completed.

Means for solving the problem d1, that is, the present invention provides a layer (a) consisting of a single layer of vinylidene fluoride resin (a1) or a laminate of a layer (a1) and a layer of thermoplastic resin (a2), Layer (a1) is placed on the surface of layer (b), which is mainly composed of at least one selected from polyamide resin, polyphenylene ether resin, polycarbonate, thermoplastic polyester resin, and rubber-reinforced styrene resin, so that layer (a1) becomes the surface layer. (a1) and (a1) which are in contact with (b) and (b),
At least one of a2) is at least one unsaturated compound (c) containing a functional group selected from a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group and an epoxy group, or a (co)polymer of (c). The present invention provides a laminate characterized by being modified by coalescence.

The present invention will be explained in detail below.

Polyvinylidene fluoride resin (a1
) is not only a homopolymer of vinylidene fluoride, but also a vinylidene fluoride content of 50 mol% or more, preferably 7
It also contains 0 mol% or more, more preferably 90 mol% or more of a copolymer. Further, a blend polymer having a vinylidene fluoride content of 75% by weight or more, which is a combination of a homopolymer or copolymer of vinylidene fluoride and a polymer of an ethylenically unsaturated carboxylic acid ester compound such as polymethacrylate, can also be suitably used.

The thermoplastic resin (a2) used in the present invention is preferably a resin that can be molded at an injection molding temperature of 350° C. or lower. For example, styrene resins such as polystyrene, high impact polystyrene, As resin, ABS resin, AASAs resin, ES resin, acrylic resins such as methyl methacrylate resin, copolymer resin of methyl methacrylate and styrene, polyethylene, polypropylene, etc. Polymers such as olefin resins, vinyl chloride resins, polycarbonate resins, polyacetal resins, polyurethane resins, ethylene-propylene block copolymers, aromatic vinyl-conjugated diene block copolymers, and 1 of these polymers. Examples include species or compositions consisting of at least two species. Furthermore, mixtures of these polymers with diene rubber, olefin rubber, elastomer, etc. can also be used.

(a2) and (b) may be the same resin, but it is preferable to use different resins because the effects of the present invention are significantly exhibited.

The polyamide as a component of the layer (b) of the present invention is usually composed of a linear diamine represented by the following formula % (wherein, X is an integer between 4 and 12) and a linear diamine represented by the following formula % formula %. (In the formula, y is an integer between 2 and 12.) Those produced by condensation with a linear carboxylic acid represented by the formula (wherein, y is an integer between 2 and 12), those produced by ring-opening polymerization of lactam, etc. can be used. Preferred examples of these polyamides include nylon 6.6, nylon 6.9, and nylon 6.10.
, nylon 6°12, nylon 6, nylon 12, nylon 11, nylon 4,6, etc.

Also nylon 6/6, 6, nylon 6/6, 10, nylon 6/12, nylon 6/6, 12, nylon 6/6
．． Copolyamides such as 6/6, 10, nylon 6/6° and 6/12 are also used.

The polyphenylene ether resin as a component of the layer (b) of the present invention is selected from, for example, the general formula (R, R'; hydrocarbon group having 1 to 8 carbon atoms;
R', R#; selected from a hydrocarbon group having 1 to 8 carbon atoms and a hydrogen atom. ) It can be obtained by oxidative coupling polymerization of a phenol compound represented by the following formula, specifically 2°6-dimethylphenol. Alternatively, a styrene resin may be added to this polyphenylene ether resin, or a modified polyphenylene ether resin modified by grafting a styrene monomer may be used.

As polycarbonate, aromatic polycarbonate,
Examples include aliphatic polycarbonate and aliphatic-aromatic polycarbonate.

Examples of the thermoplastic polyester resin include polyethylene terephthalate and polytetramethylene terephthalate.

Rubber-reinforced styrenic resins are resins that contain aromatic vinyl as an essential component reinforced with a rubbery polymer component, and are generally reinforced with aromatic vinyl as an essential component in the presence of a rubbery polymer component. It can be obtained by graft copolymerizing polymers. For example, high impact polystyrene, ABS
Examples include resin, ABS resin, and AAS resin.

Among these, polyamide resins, polyphenylene resins, and thermoplastic polyester resins are preferred in terms of heat resistance and impact resistance.

In addition, polyamide resins, thermoplastic polyester resins, and polyphenylene ether resins include diene rubbers, olefin combs such as EPRSEPT, conjugated diene-aromatic vinyl block copolymers, and ethylene-vinyl acetate copolymers. elastomers such as aromatic vinyl compound polymers,
A composition obtained by melt-mixing an aromatic vinyl compound, a copolymer of another vinyl monomer copolymerizable with the aromatic vinyl compound, and a functional group-modified product thereof such as an unsaturated carboxylic acid anhydride. It may be.

Furthermore, fillers such as glass fibers, carbon fibers, metal fibers, glass beads, asbestos, wallasnite, calcium carbonate, talc, and barium sulfate may be used alone or in combination in layer (b) as reinforcing materials.

In the present invention, a vinylidene fluoride resin (a1) sheet or (a) consisting of a vinylidene fluoride resin (a1) and a thermoplastic resin (a2) layer (
In lamination of layer a) and layer (b), layer (a1) and layer (b)
) or (a2) layer and (b) layer, a functional group-containing unsaturated compound (c) component is present in at least one of (a1), (a2), and (b). It is necessary. The unsaturated compounds used here (
Examples of c) include hydroxyl group, carboxyl group, acid anhydride group, amino group and epoxy group.

The hydroxyl group-containing unsaturated compound is a compound that has at least one unsaturated bond (double bond, triple bond) and also contains a hydroxyl group. Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and unsubstituted trivalent alcohols of unsaturated carboxylic acids. Examples include esters with hydrohydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted trihydric or higher alcohols.

Among the hydroxyl compounds used in the present invention,
Representative examples of suitable ones include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene.
butene, 3-hydroxy-2-methyl-1-propene,
cis-5-hydroxy-2-pentene, trans-5-
Hydroxy-2-pentene, cis-1,4-dihydroxy-2-butene, trans-1,4-dihydroxy-2
-butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2.3.4,
5.6-pentahydroxyhexyl acrylate), 2,
Examples include 3,4°5.6-pentahydroxyhexyl methacrylate), 2.3.4.5-tetrahydroxypentyl acrylate, and 2,3,4.5-tetrahydroxypentyl methacrylate.

These may be used alone or in combination of two or more.

Examples of carboxyl group-containing unsaturated compounds used here include acrylic acid, methacrylic acid, crotonic acid,
Examples include cinnamic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred. These may be used alone or in combination of two or more.

Examples of the unsaturated compound containing an acid anhydride group include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl succinic anhydride, and tetrahydrophthalic anhydride. Particularly preferred unsaturated acid anhydrides include Maleic anhydride.

These may be used alone or in combination of two or more.

The amino group-containing unsaturated compound has the following general formula (wherein R1 represents hydrogen, a methyl group, or an ethyl group, and R2 represents hydrogen, an alkyl group having 1 to 12 carbon atoms, or an alkanoyl group having 2 to 12 carbon atoms). A vinyl monomer having at least one amino group or substituted amino group represented by a phenyl group having 6 to 12 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, or a derivative thereof. , specific examples include alkyl acrylic acids or methacrylates such as aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate. Ester derivatives, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, anilamine, methacrylamine and N
- Allylamine derivatives such as methylallylamine,
Acrylamide derivatives such as acrylamide and N-methylacrylamide, and aminostyrenes such as p-aminostyrene are used. Among them, allylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, and the like are particularly preferably used because they can be obtained economically on an industrial scale.

These amino group- or substituted amino group-containing unsaturated compounds may be used alone or in combination of two or more.

The epoxy group-containing unsaturated compound is a compound having an epoxy group and an unsaturated group copolymerized with an olefin and an ethylenically unsaturated compound in the molecule.

Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, allyl glycidyl ether, 2-
Methyl allyl glycidyl ether, styrene-p-glycidyl ether, 3゜4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-
Examples include 1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, and p-glycidylstyrene. These can be used alone or in combination of two or more.

Preferred functional group-containing unsaturated compounds are hydroxyl group-containing unsaturated compounds and acid anhydride group-containing unsaturated compounds.

As a preferable selection of the types of resins (a2) and (b), in the case of a sheet containing only (a1) as sheet (a), (
a1) and (b). When using a laminated sheet as sheet (a), selecting a resin so that the combination of (a2) and (b) is compatible with each other will prevent changes in appearance under harsh environmental conditions. , is preferable because a molded article with less decrease in strength can be obtained.

In addition, as a method of increasing the adhesion of the laminate (a) of (a1) and (a2), the adhesion can be increased by inserting a compatible resin film between (a1) and (a2) and laminating them. An excellent laminated sheet can be obtained.

, (a1) layer or (a2) layer, and (b) layer with the functional group-containing unsaturated compound (c) component, (
A method of copolymerizing the above component (c) when producing the main component of a1) or (a2) by polymerization, or (c)
) A method of blending a homopolymer of component (c) or a copolymer of component (c) with another vinyl monomer into (a1), (a2), and (b), or in the presence of component (c) (a1), (
A method such as melt-kneading a2) or (b) in the coexistence of a peroxide as necessary. (c) Although there are no particular rules regarding the ingredients, (a1), (a2) of the present invention,
In the component (b), it is preferably 0.01 to 60% by weight, more preferably 0.1 to 20% by weight.

The method for manufacturing the sheet will be described below. A sheet containing only (a1) can be produced using an extruder or a hot roll.

Although the method for manufacturing the laminate (a) consisting of the layer (a1) and the layer (a2) is not particularly limited, examples of the lamination method are shown below.

(1) A method of producing a laminate by drawing out (a+) and (a2) in a stacked state from a molding machine such as an extruder or a hot roll.

(2) Using an extruder or hot roll, (a1), (a2)
A method of molding each of the molded products of ), overlapping each of the sheets or films of (a1) and (a2), and bonding them under heat and pressure. (a1)
(a2) An adhesive film may be inserted between the sheets and bonded under heat and pressure.

(31 A method of stacking and compression molding a sheet of (a + ) and a pellet or powder of (a2), or a sheet of (a2) and a pellet or powder of (a1).

(41(a + ) is dissolved in a suitable solvent (e.g. dimethylformamide), this solution is applied to the molded product of (a2), the solvent is evaporated off, and a laminate is obtained, or (
A method in which a solution of a2) dissolved in a suitable solvent is applied to the sheet of (a1), and the solvent is evaporated off to obtain a laminate.

(5) A method of bonding the sheet (a + ) and the sheet (a2) with an adhesive can be implemented. In terms of quality and productivity, the laminated sheet is preferably produced by methods (1) and (2), and more preferably by method (1).

In the present invention, the thickness of layer (a1) is preferably 10 to
The thickness is preferably 500 μm, more preferably 20 to 300 μm.

Further, the thickness of the laminate (a) consisting of (a1) and (a2) is preferably 1000 μm or less, more preferably 500 μm or less.

An adhesive is not particularly required between the (a) layer or (a1) layer and the (b) layer, but an adhesive may be used.

The method for applying or coloring the laminated sheet is shown below. The method of dispensing includes dispensing on at least one side of the (a1) layer, or on the (a1) layer side of the (a2) layer, or dispensing on the (a1) layer between the (a1) layer and (a2) layer.
There is a method of inserting a coated or colored film within a range that does not affect the adhesion between the layer and the (a2) layer.

The coloring can be done by adding a coloring agent, an additive, etc. to either or both of the (a1) layer and (a2) layer.

Coloring agents include titanium oxide, carbon black, cadmium red, cadmium orange, cobalt flu, cobalt purple, cobalt green, gun blue, red iron oxide, iron oxide black, cyanine blue, cyanine green, phthalocyanine green, phthalocyanine blue B1, etc. .

Examples of additives include talc, stone powder, diatomaceous earth, bentonite, graphite, calcium carbonate, alumina,
Aluminum vermilion etc.

In addition, when manufacturing the laminate of the present invention, (a
It is also possible to appropriately add a heat stabilizer, plasticizer, lubricant, ultraviolet absorber, antistatic agent, etc. to 1), (a2) or (b).

In the present invention, the layer (a) and the layer (b) can be laminated using a commonly used injection molding machine and mold. That is, a sheet-like or pre-vacuum-formed layer is placed in a mold so that the layer (a1) becomes the surface layer of the molded product, and the resin of (b) is filled into the mold to perform lamination and molding. Can be done at the same time.

Regarding the extrusion molding method, the sheet (a) can be laminated on the resin sheet extrusion or profile extrusion of (b) before or at the die exit, or it can be laminated by lamination using a pressure roll. can.

Regarding the press molding method, the sheet (a) can be placed in a press mold and laminated with the resin (b) by heat compression bonding.

The laminate obtained by the present invention has excellent properties such as weather resistance, heat resistance, scratch resistance, chemical resistance, abrasion resistance, and ease of stain removal, so it is suitable for fields where these properties are required. It can be widely used. For example, wheel-related interior and exterior parts include handle covers, front fenders, body covers, fairings, side covers, and rear cowls for motorcycles, and body outer panels, radiator grilles, emblems, foil caps, and louvers for four-wheel vehicles. , interior parts such as instrument panels and console boxes, bumpers, door mirrors, and fenders.
Can be used for exterior products such as mirrors and side moldings.

It can also be used for housings of OA equipment, home appliances, etc., as well as sanitary parts such as washstands and bathrooms, and decorative parts such as furniture construction materials.

e. Example The present invention will be explained in more detail with reference to Examples below.

Note that % means weight %.

(a) Preparation of resin (a1) sheet (1) Type: Three types of titanium oxide are added to the following two types of vinylidene fluoride resin.
A mixture of % by weight was used.

a+-1: polyvinylidene fluoride (KYNAR720,
(manufactured by Penn Ortho) a+-2: Polyvinylidene fluoride (KYNAR1120
, acrylic alloy grade 90%/(c-1) 10% melt mixture) (2) Molding method Using pellets of resin a1-1, under the following extrusion conditions,
Sheet thickness 0. A sheet with a thickness of 1 mm and a sheet width of 400 mm was obtained.

Extrusion conditions ■ Use an extruder with a screw diameter of 50 mm, a T-die, polygingerol, and a take-off device.

■Cylinder temperature 220~240℃ ■T die temperature 2
30-250℃ (b) Preparation of resin sheet (a) (1) Type and blending ratio (%) Type and blending ratio of a2 resin, and a1 resin and ′
Laminated sheet (a) with a2 resin is shown in Table 1.

(2) Molding method A) Co-extrusion molding method Using pellets prepared by melt-mixing the ingredients shown in Table 1, the surface layer is polyvinylidene fluoride resin (a+) with a thickness of 0°1 mm, and the lower layer is is 0.3m thick
Total sheet thickness 0.4 m made of thermoplastic resin (A2)
m, laminated sheet with sheet width 400ma+) (a-1), (
a-2) and (a-5) were obtained.

Extrusion conditions■ Attach a feed block to an extruder with a screw diameter of 50mm, assemble a vertical extruder with a screw diameter of 30IIIm, use a T-die, polygingerol, and a take-off device, and use a thermoplastic resin ( a2), and polyvinylidene fluoride resin (a1) was supplied to an extruder having a screw diameter of 301II11.

■ Cylinder temperature: Extruder with screw diameter of 50 mm 220-240℃ Extruder with screw diameter of 30 mm: 220-240℃ ■ T-die temperature: 230-250℃ B) Press lamination method Using pellets of (a2) resin compounding components shown in Table 1 ,
(a2) Sheet was obtained by the method shown in (2) Molding method of (a) Preparation of resin sheet.

An acrylic film with a thickness of 35μ (manufactured by Mitsubishi Rayon, acrylic plain film) was inserted as an adhesive layer between the (a1) sheet and the (a2) sheet, and the film was pressure-formed at a temperature of 210°C using a press molding machine. , a laminated sheet (a-3), (a-4) with a thickness of 0.4 mm and a sheet width-side of 350 mm.
I got it.

(c) Preparation of functional group-containing unsaturated compound (c) (1) species
Class C-1: Hydroxymethacrylate copolymer AsC-2:
Styrene-maleic anhydride copolymer (Daisoda 700
(manufactured by Arcopolymer) (2) Production of c-1 polymer After purging the inside of a stainless steel reaction vessel with a stirrer with nitrogen, 30 parts of styrene and 1 part of acrylonitrile were added in a nitrogen stream.
0 parts, 2-hydroxymethacrylate 10 parts, tert
-0.43 parts of dodecyl mercaptan, 1.0 parts of sodium dodecylbenzenesulfonate, and 140 parts of ion-exchanged water were added. While circulating hot water at 70°C through the jacket, add 0.1 part of ethylenediaminetetraacetic acid sodium salt and 1 part of sulfuric acid.
An aqueous solution consisting of 0.003 parts of iron, 0.2 parts of formaldehyde sulfoxylate dihydrate, and 15 parts of ion-exchanged water and 0.3 parts of cumene hydroperoxide were added, and after a polymerization reaction for 2 hours, 30 parts of styrene was added. parts, 10 parts of acrylonitrile, 10 parts of 2-hydroxymethacrylate, t
After adding 0.43 parts of ert-dodecyl mercaptan, 1.0 parts of sodium dodecylbenzelsulfonate, 90 parts of ion-exchanged water, and 0.3 parts of cumene hydroperoxide, the polymerization reaction was further carried out for 3 hours. A calcium chloride aqueous solution was added to the obtained polymer latex, followed by washing, dehydration, and drying to obtain c-1.

(d) FJ adjustment of resin (b) (1) Type b-1: Nylon 6 with glass fiber (Amilan CM10
0I 20G manufactured by Toshi) Colored with 3% titanium oxide.

b-2 = Mixture of nylon and polyphenylene ether resin (GTX600, manufactured by engineering plastics) b-3: Nylon 6 Note 1)/c-1 = 90/10 (%)
(Note 1; Amiran CM1017, manufactured by Toshi) b-4: Polyethylene terephthalate resin (RE500 manufactured by Toyobo) b-5 = Polycarbonate resin (702 manufactured by Mitsubishi Chemical Industries, Ltd.)
2A) b-6: ABS resin (Japan Synthetic Rubber ABSI (E)
Manufacture of laminate (1) Molding method of injection molded product■ The injection mold has a length of 350 mm and a width of 150 mm.
A rectangular sheet mold with a wall thickness of 2.5 mm was used. The gate uses a 10 mm direct gate in the center of the seat.

■ Molding method and molding conditions Sheet (a) obtained in (a) or (b) was processed in (1) above.
) was inserted into the mold. As the injection molding conditions, a 125 ton mold clamping force injection molding machine was used, and resin (b) was placed in the mold.
injection filling was performed.

Molding temperature is 270~290℃, molding pressure is 80~90k
g/cJ, injection time 10-20 seconds, cooling time 30-50
Second, the mold temperature was 80° C., and an injection molded product whose surface layer was made of vinylidene fluoride resin was obtained.

Combinations of sheet (a) and resin (b) are shown in Examples 1-4 and Comparative Examples 1-2 in Table 2. Comparative example 3 is nylon 6
The injection molded product described in the example was obtained by using a resin containing glass fibers and colored by adding 3% titanium oxide, without laminating a surface layer.

(f) Evaluation method (1) Adhesion The width of the laminated product obtained by injection molding is 10su++.

A strip-shaped specimen with a length of 50+m was cut out, and the plane (a1) and (
The a1) sides were overlapped 10 times and bonded using a cyanoacrylate resin adhesive to produce a strip-shaped test piece with incisions at both ends of the overlapped portion.

Using Autograph 15-2000 (manufactured by Shimadzu Corporation, tensile testing machine), the tensile speed was 50111! Tensile adhesive strength was measured at l/min to evaluate adhesion.

(2) Weather Resistance Using a Sunshine Weather Meter (manufactured by Suga Test Instruments), the change in appearance of the laminate after irradiation for 3000 hours was determined by the color difference (ΔE) using a Hunter color difference meter. In addition, changes in adhesion were evaluated according to the evaluation method (1).

The larger the (ΔE) value is, the greater the chromaticity color becomes, which is not preferable.

The results are shown in Table 2.

The following can be understood from the results in Table 2.

The molded products of the laminates of the present invention shown in Examples 1 to 5 have been shown to have excellent interlayer adhesion and weather resistance.

Comparative Example 1.2 did not contain the component (c) in any of the layers (a1), (a2), and (b), and therefore no adhesion was obtained.

Comparative Example 3 is a nylon 6 resin molded product, but yellowing was large in the long-term weather resistance test, indicating that the vinylidene fluoride resin laminate of the present invention is superior.

f0 Effects of the Invention The laminate of the present invention is a laminate of a sheet whose surface layer is made of vinylidene fluoride resin and a resin whose main component is polyamide and/or polyphenylene ether.

In the case of polyvinylidene fluoride resin, it has not been possible to produce a strong laminate with polyamide and polyphenylene ether resin due to poor adhesion with other resins.

However, in the present invention, this problem was solved by modifying the structure using a functional group-containing unsaturated compound.

Since the surface of the laminate is made of vinylidene fluoride resin, the molded product has excellent performance in terms of weather resistance, heat resistance, scratch resistance, chemical resistance, abrasion resistance, and ease of stain removal. It is extremely effective as an exterior component used in harsh environmental conditions.

Claims (5)

[Claims] (1) Layer (a) consisting of a single layer of vinylidene fluoride resin (a_1) or a laminate of a layer (a_1) and a layer of thermoplastic resin (a_2), a polyamide resin, a polyphenylene ether resin, a polycarbonate, (
A laminate in which the a_1) layer is the surface layer, and the (a_1) and (a) which are in contact with (b) and (b)
At least one of __2) is at least one unsaturated compound (c) containing a functional group selected from a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group and an epoxy group, or a (co)polymer of (c) A laminate characterized by being modified by coalescence. (2) The laminate according to claim (1), wherein the modification is produced by copolymerizing (c) when the main component (a_1) or (a_2) is produced by polymerization. (3) A patent claim in which the modification is a homopolymer of (c) or a copolymer of (c) and another monomer blended with (a_1), (a_2) and/or (b). Range No. 1
) The laminate described in item 2. (4) Denaturation occurs in the presence of (c) (a_1), (a_2)
The laminate according to claim (1), which is obtained by melt-kneading the main component (b). (5) The laminate according to claim (1), wherein (b) is a composition comprising nylon and a polyphenylene ether resin or a composition comprising nylon and fibers.