Moulding laminate

Abstract: A molding laminate includes a cross-linked polyolefin resin foam, a facing material laminated on the foam, and an adhesive layer adhering the foam and the facing material to each other. The adhesive layer comprises a water-based adhesive material cured by a curing agent, and is baked in advance of the inter-laminal adhesion process onto the cross-linked polyolefin resin foam and/or the facing material.

Description: The present invention relates generally to moulding laminates, and particularly to a moulding laminate comprising a resin foam and a facing material laminated thereon. Automobile interior materials such as door trim, panels, or ceilings, etc. are composed of a moulded laminate incorporating a resin foam pad, and a facing material laminated thereon. Such laminate can be moulded into desired form by, for example, a vacuum-moulding method or a stamp-moulding method. The pad and the facing material of such laminates are adhered together by an adhesive material which generally is an organic-solvent based adhesive material containing an isocyanate cross-linking agent (as disclosed for example in Japanese Patent Publication Nos. 55067/1982 and 228/1988). This type of adhesive material, however, creates environmental hazards due to the volatile solvent contained therein, and safety devices such as explosion-proof equipment would be required in a plant for manufacturing interior detail materials using such adhesives. Therefore, the practice of using water-based adhesives in place of organic-solvent based adhesives in laminates has begun. Japanese Patent Publication No. 33518/1988, for example, teaches a water-based adhesive material containing an aziridine compound as a cross-linking agent. However, the adhesive strength therein between the pad and the facing material tends to be insufficient, such that the facing material can easily peel away from the pad, particularly when the laminate is moulded into complex forms by a deep-draw moulding method, or is exposed to an atmosphere of high temperature. The present invention provides a laminate for moulding manufactured with a water-based adhesive material, and a method of manufacturing it, by which adhesive strength within the laminate can be improved. Likewise, improvement in adhesive retention in a stamp-moulded article of a laminate composed of a resin foam and a facing material adhered to each other by water-based adhesive material can also be achieved. A laminate according to one aspect of the present invention includes a cross-linked polyolefin resin foam, a facing material laminated thereon, and an adhesive layer which adheres the facing material to the cross-linked polyolefin resin foam. The polyolefin resin of the foam is a polypropylene resin optionally in combination with a polyethylene resin. The adhesive layer comprises a water-based adhesive material having been cured by a curing agent and baked prior to the inter laminate adhesion process onto the cross-linked polyolefin resin foam and/or the facing material. A method, according to another aspect of the invention, of manufacturing a laminate for a moulding, includes the steps of: providing each of (1) a cross-linked polyolefin resin foam, the polyolefin resin of which foam is as defined above and (2) a facing material; applying a water-based adhesive material containing, as a curing agent, an aziridine compound to the cross-linked polyolefin resin foam and/or facing material; drying the adhesive material; baking the adhesive material onto the cross-linked polyolefin resin and/or facing material thereby to form an adhesive layer; laminating the facing material onto the cross-linked polyolefin resin foam with the adhesive layer therebetween; and adhering the facing material to the resin foam by heat and pressure. According to yet another aspect, the invention provides a stamp-moulded article comprising a cross-linked polyolefin resin foam, the polyolefin resin of which foam is as defined above, a rigid layer thermally fused onto the foam, a facing material laminated on the foam, and an adhesive layer composed of a water-based adhesive material containing, as a curing agent, an aziridine compound, for adhering the facing material to the foam. Prior to lamination, the adhesive layer is baked on the cross-linked polyolefin resin foam and/or the facing material. According to a further aspect, the invention provides a method of manufacturing a stamp-moulded product which utilizes a moulding device having upper and lower mould-halves whereby the above-described stamp-moulded article is fashioned. This manufacturing method includes the steps of: supplying a thermoplastics resin parison into the lower mould-half; placing, on the resin parison, a laminate for moulding comprising (1) a cross-linked polyolefin resin foam, the polyolefin resin of which foam is as defined above, and (2) a facing material laminated on the foam through (3) an adhesive layer which is composed of a water-based adhesive material containing, as a curing agent, an aziridine compound, which adhesive material has been baked prior to the inter-laminate adhesion process onto the foam and/or the facing material, such that the facing material of the laminate faces the upper mould-half; and closing the moulds tightly, thereby providing the laminate and the thermoplastics resin as a single body. The foregoing and other objects and advantages of the present invention will be more fully apparent from the following detailed description, given with reference to the accompanying drawings in which: Fig. 1 is a sectional view of a part of a laminate according to an embodiment of the invention showing each layer of the laminate; Fig. 2 is a sectional view of a part of a laminate according to another embodiment of the invention showing each layer of the laminate; and Fig. 3 is a sectional view of a part of a laminate according to yet another embodiment of the invention showing each layer of the laminate. General Structure of a Laminate for Moulding The general structure of a laminate in accordance with one embodiment of the invention is illustrated by Fig. 1. The laminate 1 comprises a laminar resin foam 2, a facing material 3 laminated on the resin foam 2, and an adhesive layer 4 adhering the facing material 3 to the resin foam 2. The adhesive layer 4 is baked onto the resin foam 2 and/or the facing material 3. Referring now to Fig. 2, the structure of a laminate 1a, according to another embodiment of the invention, for moulding comprises the resin foam 2, the facing material 3, and a first adhesive layer 4a adhering the facing material 3 to the resin foam 2, likewise as above. In addition, the laminate 1a includes a second adhesive layer 5 formed on the reverse surface of the resin foam 2. In the case of this laminate 1a, the first adhesive layer 4 is baked onto the obverse surface of the resin foam 2 and/or the facing material 3, and the second adhesive layer 5 is baked onto the reverse surface of the resin foam 2. Resin Foam The resin of a foam employed in the laminate of this invention is a cross-linked polyolefin resin which is a polypropylene resin optionally in combination with a polyethylene resin. The polyethylene resin can be an ethylene homopolymer resin, or a polyethylene resin copolymerized with a substance other than ethylene, e.g., olefin vinylacetate, acrylic acid, or acrylic ester. The ethylene homopolymer resin preferably should have a density within the range of 0.897 to 0.955 g/cm 3 , and a melt index within the range of 0.5 to 55. Suitable polypropylene resins include propylene homopolymers, or copolymeric resins of propylene and ethylene, butene or a diene monomer. The most preferable polyolefin resin is a copolymer resin containing 0.5 to 35 mole percent ethylene or butene copolymerized with polypropylene. The polypropylene resin may be a random copolymer, a block copolymer, or a random block copolymer. The polyolefin resin may be cross-linked by subjecting it to irradiation, for example, with electron rays or alpha, beta or gamma particles; or by a chemical process employing a peroxide such as dicumyl peroxide; or by exposure to ultraviolet light. The foam may have a gel percent in the range of 5% to 75%, more preferably from 30% to 55%, and an apparent density of 0.5 to 0.020 g/cm 3 more preferably from 0.10 to 0.033 g/cm 3 . If the laminate is to be moulded by a stamp-moulding method, the cross-linked polyolefin resin foam may have an average gel percent in the range of 30% to 75%, more preferably from 40% to 65%, and an apparent density of 0.5 to 0.020 g/cm 3 , more preferably from 0.100 to 0.040 g/cm 3 . If the average gel percent is less than 30%, the foam may be susceptible to breakage due to the temperature of the rigid resin material, and to the moulding pressure which would need to be employed in the stamp-moulding process, resulting in unevenness in the surface of the stamp-moulded article. On the other hand, if the average gel percent is in excess of 75%, the elongation percentage of the foam is decreased such that the foam is likely break during the moulding process, making it difficult to obtain a stamp-moulded article of desired form. Furthermore if the apparent density is greater than 0.5 g/cm 3 , the textural qualities of the foam are degraded, making it unsatisfactory for use as a padding material. Conversely, if the apparent density is under 0.02 g/cm 3 , the rigidity of the foam is decreased such that it may be easily broken during the moulding process. The term "gel percent" referred to above is a value which signifies the percentage by weight of insoluble substance in proportion to the initial weight of a specimen (0.1g) of a foam after soaking the specimen in tetralin at 130°C for three hours. The apparent densities cited above are values in accordance with Japan Industrial Standard-K6767. The laminal thickness of the cross-linked polyolefin resin foam is usually in a range of from 1.0 to 10.0 mm. The thickness may be suitably chosen according to the purposes for which the laminate will be used. If the laminate is to be moulded by a stamp-moulding method, the foam preferably has a thickness of 0.5 to 10 mm. Facing Material The laminate facing material may, for example, cover the surface of the resin foam. Suitable facing materials include natural or synthetic fiber webbing, synthetic resin composed principally of polyvinyl chloride resin, thermoplastic elastomer, or leather, the choice of which depends on how the laminate is to be employed. The thickness of the facing material normally should be of the order of 0.2 to 2.0 mm. When the laminate is to be stamp-moulded, the facing material can have a 100%-elongation stress at 25°C of less than 150 kg/cm 2 , preferably within the range of 25 kg/cm 2 to 120 kg/cm 2 . If the stress rating is greater than 150 kg/cm 2 , the facing material is susceptible to breakage during the moulding process, as is the surface of the foam opposite the facing material. The 100%-elongation stress is rated according to JIS-K6767. Adhesive Layer The adhesive layer comprises a water-based adhesive material containing a curing agent, which curing agent is an aziridine compound. The adhesive material may be, for example, an emulsion of acrylic resin or urethane resin containing polar elements. The polar elements are polar functional groups having a general structure which can be represented as follows: -O-, -NH- and Examples of suitable acrylic resin include an acrylic copolymer of, for example, 2-ethylhexylacrlate, methyl methacrylate, acrylic acid, styrene, 2-hydroxyethyl methacrylate, butylacrylate, ethylacrylate or acrylamide. Such acrylic resins can be obtained by emulsion polymerization. A urethane resin which can be employed can comprise a polyisocyanate and a compound having polar groups such as a polyester, polyether or polyetherester. The polyester can be, for example, a condensation product obtained from a saturated or unsaturated polybasic carboxylic acid such as adipic acid, succinic acid, maleic anhydride or sebacic acid, or an acid anhydride thereof, and polyhydric saturated alcohols, polyalkyleneglycols, or mixtures thereof. The polyhydric saturated alcohols can be ethyleneglycol, propyleneglycol, tetramethyleneglycol, trimethylolpropane, 1,6-hexanediol and 1,4-butanediol. The polyalkyleneglycols can be polyethylene glycol, polypropylene glycol, and polytetramethylene glycol of relatively low molecular weight. The polyether can be an alkylene oxide such as ethylene oxide or propylene oxide, a polymerized product such as styrene oxide or epichlorohydrine, and a random or block copolymer thereof, or an additional polymer of such materials compounded with polyhydric alcohols. The polyetherester can be, for example, a product obtained by adding an epoxy compound such as ethylene oxide or propyleneoxide to the aforementioned polyester. The polyisocyanate can be an aromatic diisocyanate such as tolylenediisocyanate and an isomer thereof or 4,4-diphenylmethane diisocyanate, an aromatic aliphatic diisocyanate such as xylylene diisocyanate, an aliphatic diisocyanate such as hexamethylenediisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, and other polyisocyanates obtained by adding trimethylol propane or its equivalent to the aforementioned diisocyanates. Such polyisocyanates may be used singly or in combination. Other urethane resins may be used, for example, as disclosed in Japanese Patent Publication No. 224192/1967 or 38760/1978, or JP-A-126795/1975. A suitable urethane resin can be emulsified by dispersing the urethane resin in water using an emulsifying agent. A water-based urethane resin having molecular ends comprising hydroxyl or carboxyl groups may be substituted for the urethane resin emulsion. Other water-based urethane resins may be used in which the composition of the source materials is adjusted to yield molecular ends having isocyanate groups blocked by such salts as bisulfite bases. The above-described acrylic adhesive materials or urethane adhesive materials may be used singly, or in mixed form, in which case the drying and adhering properties can be adjusted to suit requirements. Water-soluble aziridine curing agents are suitable for incorporation into the water-based adhesive material Water-dispersions of aziridine compounds may be used as the aziridine curing agent. Such aziridine compounds can have two or more aziridine rings, for example (a) 4,4'-bis(ethyleniminocarbonylamino)diphenylmethane, or (b) 2,2'-bishydroxymethyl-butanol-tris[3-(1-aziridinyl)propionate]. Two or more of this class of aziridine compounds may be used in combination. Aziridine compounds (a) and (b) above are represented by the following general structural formulae: Aziridine compounds are generally insoluble in water, and therefore prior to use they are forcedly dispersed in water, using a small quantity of an emulsifying agent, after having been temporarily dissolved in a solution of dimethylsulfoxide or dimethylformamide. The aziridine curing agent which reacts with the above-described acrylic resin or urethane resin can form cross-linking structures such as those indicated below. (In the following configurations "Poly" represents a polymer chain.) The mixing ratio (A:B) of the water-based adhesive agent (A) and the curing agent (B) expressed as percent solid should be within the range from 100:1 to 100:20, and preferably within the range from 100:5 to 100:15. For moulding by the stamp-moulding method, the preferred range is from 100:8 to 100:15. Moulding Laminate Manufacturing Method This may be carried out as follows. The cross-linked polyolefin resin foam and the facing material are prepared initially. Then, a water-based adhesive containing a curing agent is applied to the surface of the foam and/or the facing material to be adhered using, for example, a wire coater, a doctor knife, a roll coater or a reverse coater. Normal coverage during application is from 5 to 200 g/m 2 . The viscosity of the water-based adhesive is preferably adjusted to be within 8000 to 12000cps (8 to 12 Pa.s) using a thickener such as a polycarboxylic acid polymer or carboxymethyl cellulose in order to optimize efficiency on application. The applied water-based adhesive material is dried and then is baked onto the surfaces to be adhered, forming an adhesive layer on the foam and/or the facing material. Sufficient adhesive strength between the foam and the facing material is not achieved if the adhesive material is not baked on or is dried only by using a hot air fan or the like. The baking process is preferably carried out using an infrared heater, in which case the average wavelength of the irradiating rays should be within the range of 0.75 to 1000 µm, more preferably in the range of 2 to 14 µm. The surface temperature during the baking process should be within the range of 60°C to the melting point of the resin component of the foam, preferably within the range of 90 to 140°C. If the surface temperature during baking is too low, then insufficient adhesive strength results. Conversely, if the surface temperature is too high, the surface of the foam tends to become rough, deteriorating the quality of the manufactured product. The foam and the facing material are then placed together in contact through the adhesive layer. When this sandwich of materials is heated at 50 to 100°C and compressed, a laminate as shown in Fig. 1 is obtained. If an adhesive layer is formed onto the reverse surface of the foam as well, a laminate as shown in Fig. 2 is obtained. This adhesive layer can be formed according to the method described above, in which a predetermined quantity of a water-based adhesive material applied to the foam is dried and baked under infrared-ray radiation. In a specific method of laminate manufacture according to the present invention, a soft sheet of polyvinyl chloride resin 0.7 mm in thickness is employed as the facing material, and a foamed polyolefin resin 3 mm in thickness having a gel percent of 40% and an apparent density of 0.050 g/cm 3 is employed as the foam material. A water-based adhesive material is prepared by adding a water-dispersion of an aziridine curing agent in an amount of 10 parts by weight to an active hydrogenate emulsion in an amount of 100 parts by weight. It is then applied to at least one of the interfacial surfaces of the foam and the facing material in an amount per unit area of 50 g/m 2 . Next, the water in the adhesive material is evaporated at 90 to 150°C, and the adhesive material is baked using an infrared heater. Subsequently, the facing material and the foam are heated to 50° to 100°C and compressed, whereby the facing material and the foam are adhered. Additionally, an adhesive material is applied to the reverse surface of the foam, and the water therein is evaporated, after which the adhesive material is baked onto the foam. Utilization of a Moulding Laminate A laminate according to the present invention can be moulded into desired forms such as instrument panels, door trims or ceilings of automobile interiors using, for example, a vacuum-moulding method or a compression-moulding method. Automobile interior articles fashioned of a moulded laminate as shown in Fig. 2 are easily fitted into designated regions of doors, ceilings and the like by virtue of the adhesive layer formed on the foam. Stamping Moulded Product A laminate manufactured according to this invention can be moulded into a desired form using a stamp-moulding method. Such a stamp-moulded article is, in part, illustrated in cross section in Fig. 3. The stamp-moulded article 10 principally comprises a laminate 11 and a rigid layer 12 reinforcing the moulded foam of the laminate 11. The laminate 11 is formed as described above and is composed principally of a resin foam sheet 2, a facing material 3 laminated onto the resin foam 2, and an adhesive layer 4 adhering the facing material 3 to the resin foam 2. The rigid layer 12 is formed of a thermoplastics resin which is thermally fused to the resin foam 2 of the laminate 11. Rigid Layer Examples of thermoplastics resins which can comprise the rigid layer include alpha olefin polymer resins such as polyethylene resin, copolymer resins of ethylene and alpha olefin (e.g., straight-chain polyethylene resins of low density, intermediate density or high density polymers comprising copolymers of ethylene and alpha olefin); or polyethylene resins copolymerized with a monomer such as vinylacetate, acrylic acid, or acrylic ester. These thermoplastics resins may be utilized singly or in combination. Those particularly preferable are resins containing ethylene, propylene or butene homopolymers, as well as resins containing random, block, or random-block copolymers of these homopolymers. Extenders, thickeners, dyes, antioxidants or stabilizers, for example, may be added to the thermoplastics resin. Method of Manufacturing Stamp-Moulded Article An illustrative method of fashioning a stamp-moulded article as described above is as follows. First, a block or sheet parison of the thermoplastics resin constituting the rigid layer is set into the lower mould-half of a moulding device. The temperature of the thermoplastics resin therein is normally about 180 to 220°C, depending on the resin substance. A laminate as described above is set onto the thermoplastics resin in the lower mould such that the facing material of the laminate faces the upper mould-half. The laminate is normally utilized at room temperature; however, the laminate may be heated. The mould halves of the moulding device are closed by pressing the upper mould against the lower mould and moulding the laminate into a predetermined form. At the same time, the thermoplastics resin parison is fused to the resin foam of the laminate, whereby the thermoplastics resin forming the rigid layer and the laminate are integrally adhered to each other to thus fashion the stamp-moulded article. The mould closure pressure is normally about 30 to 120 kg/cm 2 . The stamp-moulded article can be utilized, for example, in the interior of automobiles as a door trim, ceiling or floor material. The adhesive strength between the resin foam 2 and the facing material 3 of a stamp-moulded article formed of the above-described laminate, is high. The resin foam 2 and the facing material 3 thus remain stably adhered to each other even if the stamp-moulded article is fashioned into a complicated form by a deep-draw moulding method. Due to the fact that the average gel percent of the resin foam and the elongation stress of the facing material are within the previously mentioned ranges, wrinkles or milkiness in the facing material are averted, and the laminate is of excellent appearance. According to the foregoing method, the thermoplastic resin is set into the lower mould-half of the molding device, but it may also be set into the upper mould-half. The moulding device may be of any form having at least a pair of mould sections. For example, a pair of moulds operating laterally may be used. A method of manufacturing a stamp-moulded article will now be described in greater detail. A soft polyvinyl chloride sheet (0.45 mm in thickness) with a 100%-elongation stress of 135 kg/cm 2 is used as the facing material, and a polyolefin resin foam, comprising 82 parts by weight polypropylene resin, including 5% random copolymer of ethylene, and a straight-chain polyethylene resin in an amount of 18 parts by weight and having a density of 0.918 g/cm 3 and a melt index of 8, is used as the foam. A water-based adhesive material comprising an emulsion in an amount of 100 parts by weight containing active hydrogen and a water-dispersion aziridine curing agent (Chemitite DZ-22) in an amount of 10 parts by weight added thereto is prepared, and is applied to at least one of the inter-laminal surfaces of the foam and the facing material in an amount per unit area of 50 g/m 2 (wet). The adhesive material is then dried, and is baked using an infrared heater (of the Inconel type). The surface temperature of the adhesive material during baking reaches 100 to 120°C. Next, the heated facing material is laminated onto the foam, and the laminate is heated to 50 to 100°C and compressed in order to adhere the laminate. The thermoplastics resin constituting the rigid layer is set on the surface of the foam of the laminate thus obtained, and, employing the stamp-moulding method, the final article is manufactured. The following Examples illustrate preferred embodiments of the method of the invention. All parts and percentages are by weight unless otherwise indicated. Some Comparative Examples (3 and 6) show that when using a solvent based adhesive outside the invention, poor results are obtained. The remaining Comparative Examples show that poor results may also be obtained if the preferred conditions for carrying out the invention are not followed. Example 1 A water-based adhesive emulsion was prepared by mixing 100 parts of an acrylic resin emulsion (45% solid) containing hydroxyl groups and carboxyl groups, and 10 parts of an aziridine compound, namely 4,4'-bis(ethyleniminocarbonylamino)diphenylmethane (Japan Syokubai Kagaku Kogyou Co. Chemitite DZ-22). A thickener (Kao Co. Bissurf F) was added to the emulsion, so as to yield an adhesive material of 5000cps (5 Pa.s) viscosity. The adhesive thus prepared was applied in an amount per unit area of 50 g/m 2 to one principal surface of a polypropylene resin foam having an apparent density of 0.067 g/cm 3 by the gravure roll method. The adhesive material was then baked using an infrared heater. Next, a sheet of blended resin, comprising polyvinyl chloride resin and ABS resin of 0.7 mm thickness, was laminated at a surface temperature of 80°C on the foam adhesive layer and pressed against it to produce a laminate for moulding. Example 2 A laminate was manufactured in the same manner as in Example 1, except that a polypropylene resin foam having an apparent density of 0.050 g/cm 3 was used instead. Example 3 A water-based adhesive emulsion was manufactured by mixing 60 parts of a (50% solid) urethane resin emulsion containing hydroxyl groups and carboxyl groups, 60 parts of an acrylic resin emulsion as used in Example 1, and 10 parts of an aziridine compound as used in Example 1. A thickener was added to the emulsion, so as to yield an adhesive material of 8000cps (8.Pa.s) viscosity. The water-based adhesive material thus prepared was applied in an amount per unit area of 50 g/m 2 to the principal surface of a polypropylene resin foam having an apparent density of 0.050 g/cm 3 by the doctor knife method, and the adhesive layer formed was dried and was baked using an infrared heater. Next, a polyvinyl chloride resin sheet 0.45 mm in thickness was laminated at a surface temperature of 80°C on the foam adhesive layer, and pressed against it, to produce a laminate for moulding. Example 4 A laminate was manufactured in the same manner as in Example 1, except that the surface temperature during the infrared-ray baking process was 130°C instead. Comparative Example 1 A laminate for moulding was manufactured in the same manner as in Example 1, except that the surface temperature during the infrared-ray baking process was 50°C instead. Comparative Example 2 A laminate for moulding was manufactured in the same manner as in Example 1, except that a hot air-drying process was carried out in place of the infrared-ray baking process. Comparative Example 3 A laminate for moulding was manufactured in the same manner as in Example 1, except that saturated polyester and isocyanate were used as the adhesive material and the curing agent respectively, and that the mixing ratio of the adhesive material and the curing agent was 100:10. Evaluation A Various tests were carried out with respect to the laminates manufactured in Examples 1 to 4 and Comparative Examples 1 to 3. Detailed accounts of the tests are given below. Tables 1 and 2 show the test results. (1) Adhesive Strength Test Specimens were prepared by cutting each of the laminates into small strips 25mm in width. These specimens were subjected to 180° peel tests at room temperature (23°C), as well as a high temperature (120°C), using an autograph. The peeling speed was set to 500 mm/min. The criteria of the evaluation are indicated in the tables as follows. ○: Disruption did not occur in the adhesive layer. ▵: A partial disruption occurred in the adhesive layer. X: Disruption occurred in the adhesive layer. A dash indicates that measurement of the peeling strength was not feasible. (2) Moulding Processability Specimens equivalent to those used in the adhesive strength test were prepared, and were then heated at 160 to 180°C. The heated specimens were vacuum-moulded using a female mould having a diameter (D) of 50mm and a variable depth (H), and then the condition of the specimens thus moulded was evaluated. The criteria of the evaluation are as indicated below. ○: Disruption did not occur in the facing material nor the foam, and the adhesive layer did not peel. ▵: The adhesive layer did not peel, but the neither portion of the foam was partially fractured. X: The adhesive layer did not peel, but the foam was broken. PEELED-OFF STATE OF ADHESIVE VACUUM MOLDING PROCESSABILITY (D VALUE: mm) ROOM TEMPERATURE 120 °C 50 60 70 EXAMPLE 1 ○ ○ ○ ○ ○ EXAMPLE 2 ○ ○ ○ ○ ○ EXAMPLE 3 ○ ○ ○ ○ ○ PEELED-OFF STATE OF ADHESIVE PEELING STRENGTH (kg/25mm) SOLVENT ROOM TEMPERATURE 120°C ROOM TEMPERATURE 120°C EXAMPLE 1 ○ ○ 3.59 1.19 WATER EXAMPLE 4 ○ ○ 3.57 1.18 WATER COMPARATIVE EXAMPLE 1 ▵ ▵ 3.56 1.19 WATER COMPARATIVE EXAMPLE 2 X X - - WATER COMPARATIVE EXAMPLE 3 ○ ○ 3.58 1.17 ORGANIC SOLVENT Example 5 An emulsion (100 parts) of an acrylic resin (45% solid) containing hydroxyl groups and carboxyl groups, and 10 parts of aziridine compound, namely 4,4'-bis(ethyleniminocarbonylamino)diphenylmethane) Nihon Shokubai Kagaku Kogyou Co. Chemitite DZ-22) were mixed, and a thickener was added to the mixture to adjust the viscosity to 8000 cps (8 Pa.s), whereby an emulsion-type water-based adhesive material was manufactured. This water-based adhesive material was applied in an amount of 50 g/m 2 to the principal surface of a polypropylene resin foam having a gel percent of 53% and an apparent density of 0.067 g/cm 3 by the gravure roll method. Then, the applied adhesive material was dried, and was baked using an infrared heater. A polyvinyl chloride resin sheet 0.5 mm in thickness at a surface temperature of 80°C having a 100%-elongation stress of 100 kg/cm 2 at 25°C was laminated on the adhesive layer and pressed against it, producing a laminate for stamp-moulding. Three types of mould were employed, having boxlike upper and lower moulding portions each of 35cm square in horizontal section the lateral sides of which were at right angles, beveled at 60°, and beveled at 45°, respectively, in order to manufacture stamp-moulded articles from the laminates. A rigid material resin containing 80 wt. percent polypropylene resin and 20 wt. percent thickener was set into the lower mould-half of each mould, each of which was closed under a pressure of 50 tons. Example 6 A stamp-moulded article was manufactured in the manner according to Example 5, except that a soft polyvinyl chloride resin sheet having a 100%-elongation stress of 145 kg/cm 2 at 25°C was used. Comparative Example 4 A stamp-moulded article was manufactured in the same manner as in Example 5, except that a soft polyvinyl chloride resin sheet with a 100%-elongation stress of 159 kg/cm 2 at 25°C was used. Comparative Example 5 A stamp-moulded article was manufactured likewise as in Example 5, except that a soft polyvinyl chloride resin sheet with a 100%-elongation stress of 170 kg/cm 2 at 25°C was used. Example 7 A water-based adhesive material was prepared by mixing 40 parts of a urethane resin emulsion (55% solid) containing hydroxyl groups and carboxyl groups, 60 parts of an acrylic resin emulsion, and 10 parts of an aziridine compound (as used in Example 5) and the viscosity of the mixture was adjusted to 10,000cps (10 Pa.s) by the addition of a thickener. The water-based adhesive material was applied is an amount per unit area of 60 g/m 2 to the principal surface of a polypropylene resin foam having a gel percent of 54% and an apparent density of 0.050 g/cm 3 using the doctor knife method. The adhesive material thus applied was dried, and was baked using an infrared heater, to form an adhesive layer. A soft sheet consisting of a mixture of polyvinyl chloride resin and ABS resin 0.4 mm in thickness and having a 100%-elongation stress of 142 kg/cm 2 at 25°C, the surface of which was heated to 80°C, was laminated on the adhesive layer and was pressed against it to produce a laminate for stamp-moulding. Using the same three types of mould employed in Example 5, stamp-moulded articles were manufactured from the laminates under the same conditions as in Example 5. Comparative Example 6 An adhesive material was prepared by mixing an isocyanate with a saturated polyester adhesive agent in the ratio of 100:10. This adhesive material was applied in an amount per unit area of 60 g/m 2 to the principal surface of a polypropylene resin foam of 54% gel percent and apparent density of 0.050 g/cm 3 , using the doctor knife method. The applied adhesive material was dried, and was baked using an infrared heater, thus forming an adhesive layer. A soft sheet consisting of a mixture of polyvinyl chloride resin and ABS resin 0.4 mm in thickness having a 100%-elongation stress of 142 kg/cm 2 at 25°C was laminated at a surface temperature of 80°C on the adhesive layer and pressed against it, producing a laminate for stamp-moulding. Then, by using the same three types of mould employed in Example 5, stamp-moulded articles were manufactured from the laminates under the same conditions as in Example 5. Evaluation B The stamp-moulded articles produced in Examples 5 to 7 and Comparative Examples 4 to 6 were subjected to various relevant tests, as described below in detail. Tables 3 and 4 show the results of the tests. (1) Disruption of Pad Material (Resin Foam) and Interlaminal Peeling Disruption of the pad, and inter-laminal peeling of the facing material from the pad material were examined. The criteria of the evaluation were as follows. ○ : No disruption nor inter-laminal peeling ▵ : No practical degradation, although the disruption ratio of the pad material was 70% or more. X : Disruption and/or inter-laminal peeling occurred. (2) Wrinkles at Corners The presence or absence of wrinkles at corners of the article was examined. The criteria of the evaluation were as follows. ○ : No wrinkles. ▵ : Some wrinkles. X : Many wrinkles. (3) Milkiness at Corners The corners of the articles were examined for milkiness in each of the cases in which the boxlike molds having lateral-side angles of 90°, 60° and 45° were used. The criteria of the evaluation were as follows. ○ : No milkiness. ▵ : Some milkiness. X : Conspicuous milkiness. (4) Elongation Ratio of Adhesive Layer A laminate for stamp-moulding according to the present invention was manufactured, and was cut into small strips 30 mm in width, and a uni-directional stress was applied to each strip using an autograph, whereby they were subjected to elongation. The point at which disruption occurred in the adhesive layer was regarded as the limit point of elongation of the adhesive layer, and thus the elongation percentage of the adhesive layer was recorded at that point. Since it is not necessary to take into account temperature adaptability for the stamp-moulding method, the measurement was made at room temperature (25°C). (5) Adhesive Layer Conditions at Corners of Moulded Article: The condition of the adhesive layer at the corners of the molded article was examined in each of the cases in which the boxlike molds having lateral side angles of 90°, 60°, and 45° was used. The criteria of the evaluation were as follows. ○ : The adhesive layer did not peel. ▵ : The adhesive layer peeled partially. X : The adhesive layer peeled. (6) Adhesive Strength Specimens were prepared by cutting the laminate into small strips 25 mm in width. 180° peel tests were carried out on these specimens at room temperature (23°C) and at high temperature (120°C) using an autograph, and the adhesive strength and adhesive property of each specimen were evaluated. The criteria of the evaluation were as follows. ○ : The adhesive layer did not peel. X : The adhesive layer peeled. DISRUPTION OF PAD MATERIAL AND INTERLAMINAL PEELING WRINKLES AT CORNERS MILKINESS AT CORNERS 90° 60° 45° EXAMPLE 5 ○ ○ ○ ○ ○ EXAMPLE 6 ○ ○ ○ ○ ○ COMPARATIVE EXAMPLE 4 ○ ▵ X ○ ○ COMPARATIVE EXAMPLE 5 ○ X X X ○ ADHESIVE MATERIAL ELONGATION OF ADHESIVE LAYER(%) CONDITIONS OF ADHESIVE LAYER AT CORNERS ADHESIVE STRENGTH PEELING STRENGTH (kg/cm 2 ) 90° 60° 45° EXAMPLE 7 WATER-BASED 165 ○ ○ ○ ○ 3.57 COMPARATIVE EXAMPLE 6 ORGANIC SOLVENT 78 X ▵ ○ ○ 3.51

Claims: A laminate for moulding comprising a cross-linked polyolefin resin foam, the polyolefin resin of which foam is a polypropylene resin optionally in combination with a polyethylene resin; a facing material laminated on the cross-linked polyolefin resin foam; and an adhesive layer for adhering the facing material to the cross-linked polyolefin resin foam, the adhesive layer comprising a water-based adhesive material containing, as a curing agent, an aziridine compound, and baked in advance of the inter-laminal adhesion process onto the cross-linked polyolefin resin foam and/or facing material. A laminate according to claim 1, wherein the mixing ratio of the water-based adhesive material to the curing agent in the adhesive layer is in a range of from 100:1 to 100:20. A laminate according to claim 1 or 2, wherein the cross-linked polyolefin resin foam has a gel percent ranging from 5% to 75%. A laminate according to claim 1, 2 or 3, wherein the cross-linked polyolefin resin foam has an apparent density ranging from 0.5 to 0.050 g/cm 3 . A laminate according to any preceding claim, wherein the cross-linked polyolefin resin foam has a thickness of from 1.0 to 10.0 mm. A laminate according to any preceding claim wherein the cross-linked polyolefin resin of the foam is a polypropylene resin in combination with a polyethylene resin. A laminate according to claim 6, wherein the polyethylene resin is an ethylene homopolymer. A laminate according to claim 6 or 7, wherein the polyethylene has a density ranging from 0.897 to 0.955 g/cm 3 , and a melt index ranging from 0.5 to 55. A laminate according to claim 6, wherein the polyethylene resin is a polyethylene copolymer resin. A laminate according to any preceding claim, wherein the polypropylene resin is a propylene homopolymer resin. A laminate according to any one of claims 1 to 9, wherein the polypropylene resin is a polypropylene copolymer resin. A laminate according to claim 11, wherein the polypropylene copolymer resin is a copolymer of ethylene or butene, in an amount of 0.5 to 35 mole percent, with propylene. A laminate according to any preceding claim, wherein the cross-linking of the cross-linked polyolefin resin foam is effected by irradiation. A laminate according to any one of claims 1 to 12, wherein the cross-linking of the cross-linked polyolefin resin foam is effected chemically using a peroxide. A laminate according to claim 13, wherein the cross-linking of the cross-linked polyolefin resin foam is effected by ultraviolet irradiation. A laminate according to any preceding claim, wherein the facing material has a thickness of from 0.2 to 2.0 mm. A laminate according to any preceding claim, wherein the water-based adhesive material is an emulsion selected from acrylic resins having polar groups and urethane resins having polar groups. A laminate according to any preceding claim, wherein the aziridine curing agent is a compound having two or more aziridine rings. A laminate according to claim 17 or 18, wherein the water-based adhesive material is a water-based urethane resin. A laminate according to any preceding claim, wherein the adhesive layer is not broken in 180° peeling strength tests at room temperature and at 120°C. A method of manufacturing a laminate for a moulding, which method comprises the steps of: providing each of (1) a cross-linked polyolefin resin foam, the polyolefin resin of which foam is a polypropylene resin optionally in combination with a polyethylene resin, and (2) a facing material; applying a water-based adhesive material containing, as a curing agent, an aziridine compound to the cross-linked polyolefin resin foam and/or facing material; drying the water-based adhesive material; baking the water-based adhesive material onto the cross-linked polyolefin resin foam and/or facing material, thereby forming an adhesive layer; laminating the facing material to the cross-linked polyolefin resin foam with the adhesive layer therebetween by heating the cross-linked polyolefin resin foam and the facing material, and pressing the same against each other. A method according to claim 21, wherein the water-based adhesive material is applied to the cross-linked polyolefin resin foam. A method according to claim 21 or 22, wherein the amount of the water-based adhesive material applied is from 5 to 200 g/m 2 . A method according to any one of claims 21 to 23, wherein the temperature for baking the water-based adhesive material is set such that the surface temperature of the cross-linked polyolefin resin foam and/or facing material is from 70 to 150°C. A method according to any one of claims 21 to 24, wherein the step of baking the water-based adhesive material is performed using an infrared heater. A method according to claim 25, wherein the average wavelength of the rays from the infrared heater ranges from 0.75 to 1,000 µm. A method according to any one of claims 21 to 26, wherein the cross-linked polyolefin resin foam and the facing material are heated at 50°C to 100°C during the laminating and pressing step. A stamp-moulded product comprising: a cross-linked polyolefin resin foam, the polyolefin resin of which foam is a polypropylene resin optionally in combination with a polyethylene resin; a rigid layer thermally fused to the cross-linked polyolefin resin foam; a facing material laminated on the cross-linked resin foam; and an adhesive layer comprising a water-based adhesive material containing, as a curing agent, an aziridine compound, for adhering the facing material to the cross-linked polyolefin resin foam, the adhesive layer having been baked in advance of the inter-laminal adhesion process onto the cross-linked polyolefin resin foam and/or facing material. A stamp-moulded product according to claim 28, wherein the rigid layer comprises a thermoplastics resin. A stamp-moulded product according to claim 29, wherein the thermoplastics resin is a homopolymer selected from polyethylene resin, polypropylene resin and polybutene resin. A stamp-moulded product according to claim 29, wherein the thermoplastics resin is a copolymer comprising two or more substances selected from ethylene, propylene and butene. A stamp-moulded product according to any one of claims 28 to 31, wherein the water-based adhesive material and the curing agent are present in the adhesive layer, at a mixing ratio of the said adhesive: curing agent, in a range of from 100:1 to 100:20. A stamp-moulded product according to any one of claims 28 to 32, wherein the cross-linked polyolefin resin foam has a gel percent ranging from 40% to 65%. A stamp-moulded product according to any one of claims 28 to 33, wherein the cross-linked polyolefin resin foam has an apparent density ranging from 0.100 to 0.040 g/cm 3 . A stamp-moulded product according to any one of claims 28 to 34, wherein the cross-linked polyolefin resin foam has a thickness of from 1.0 to 10.0 mm. A stamp-moulded product according to any one of claims 28 to 35, wherein the cross-linked polyolefin resin of the foam is a polypropylene resin in combination with a polyethylene resin. A stamp-moulded product according to claim 36, wherein the polyethylene resin is an ethylene homopolymer. A stamp-moulded product according to claim 37, wherein the polyethylene has a density ranging from 0.897 to 0.955 g/cm 3 and a melt index ranging from 0.5 to 55. A stamp-moulded product according to claim 36, wherein the polyethylene resin is a polyethylene copolymer resin. A stamp-moulded product according to any one of claims 32 to 39, wherein the polypropylene resin is a propylene homopolymer. A stamp-moulded product according to any one of claims 32 to 39, wherein the polypropylene resin is a polypropylene copolymer resin. A stamp-moulded product according to claim 41, wherein the polypropylene copolymer resin is a copolymer of ethylene or butene, in an amount of 0.5 to 35 mole percent, with propylene. A stamp-moulded product according to any one of claims 28 to 42, wherein the cross-linking of the cross-linked polyolefin resin foam has been effected by irradiation. A stamp-moulded product according to claim 43, wherein the cross-linking of the cross-linked polyolefin resin foam has been effected by ultraviolet irradiation. A stamp-moulded product according to any one of claims 28 to 42, wherein the cross-linking of the cross-linked polyolefin resin foam has been effected chemically using a peroxide. A stamp-moulded product according to any one of claims 28 to 45, wherein the facing material has a 100%-elongation stress in a range of from 150 to 25 kg/cm 2 at 25°C. A stamp-moulded product according to any one of claims 28 to 46, wherein the facing material has a thickness of from 0.2 to 2.0 mm. A stamp-moulded product according to any one of claims 28 to 47, wherein the water-based adhesive material is an emulsion selected from acrylic resins having polar groups and urethane resins having polar groups. A stamp-moulded product according to any one of claims 28 to 48, wherein the aziridine curing agent is a compound having two or more aziridine rings. A stamp-moulded product according to any one of claims 28 to 49, wherein the adhesive layer is not broken in 180° peeling strength tests at room temperature and at 120°C. A method of manufacturing a stamp-moulded product employing a pair of mould-halves, comprising the steps of: supplying a thermoplastics resin parison into one of the mould-halves; placing, on the thermoplastics resin, a laminate comprising (1) a cross-linked polyolefin resin foam, the polyolefin resin of which foam is a polypropylene resin optionally in combination with a polyethylene resin, (2) a facing material laminated on the foam, and (3) an adhesive layer adhering the foam and the facing material to each other, the adhesive layer comprising a water-based adhesive material containing, as a curing agent, an aziridine compound, and having been baked in advance of the inter-laminal adhesion process onto the foam and/or facing material, the laminate being positioned such that the facing material faces the other mould-half; and closing the mould-halves tightly under pressure, thereby providing the laminate and the thermoplastics resin as a single body. A method according to claim 51, wherein the temperature of the thermoplastics resin parison is 180°C to 220°C. A method according to claim 52, wherein the pressure under which the mould-halves are closed is set within a range of from 30 to 120 kg/cm 2 .

Inventors: AKIMARU FUSAYOSHI, NAKAE TOSHIHARU, OKUBO SYUNJI, TOGO MASAYUKI, WADA OSAMU, AKIMARU, FUSAYOSHI, NAKAE, TOSHIHARU, OKUBO, SYUNJI, TOGO, MASAYUKI, WADA, OSAMU, TOGO, MASAYUKI TORAY INDUSTRIES, INC
Applicants: TORAY INDUSTRIES, TORAY INDUSTRIES, INC.
Application year: 1991
Main classification: B32B5
IPC codes: B32B5