JP4428764B2 - Soft resin material composite molded body - Google Patents

Description

【図面の簡単な説明】
【図１】本発明における、一方の表面に低表面エネルギー物質よりなる保護層を形成した熱可塑性樹脂フィルムを該保護層が最外層となるように軟質樹脂材料成形体表面に積層してなる軟質樹脂材料複合成形体の代表的な形状を示す図である。
【図２】本発明における、軟質樹脂材料複合成形体が保護層を最外層として硬質材料からなる構造体表面に積層してなる複合構造体の代表的な形状を示す図である。
【符号の説明】
１ 軟質樹脂材料成形体
２ 熱可塑性樹脂フィルム
３ 保護層
４ 硬質材料[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel soft resin composite molded body having a layer made of a low surface energy material such as a silicone resin on the surface. Specifically, it is a soft resin material composite molded body that can exhibit excellent scratch resistance and antifouling properties over a long period of time by having a low surface energy substance uniformly and extremely stably on the surface.
[0002]
[Prior art]
Conventionally, since soft resin materials have moderate elasticity, automotive interior materials and handle materials such as handles that require functionality such as soft touch or shock absorption, surface materials for home appliances bodies, grips, etc. It is used for a wide range of applications.
[0003]
However, a structure having a soft resin material as a surface layer portion is inferior in scratch resistance on the surface because the soft resin material has low hardness, and has antifouling properties against oil-based components such as oils, oil-based inks, and dirt. There was a drawback of being low. Furthermore, there is a problem that the surface itself may be contaminated by precipitation of substances such as low molecular weight components contained in the soft resin material. In particular, these solutions are desired in the above-mentioned applications in which appearance is important and design is required. It was rare.
[0004]
Up to now, as a method for improving the above problems, after molding a soft resin material molded body, a curing component is applied to the surface of the resulting molded body and subjected to curing treatment with heat, ultraviolet rays, electron beam, etc. (hereinafter referred to as coating) Process).
[0005]
[Problems to be solved by the invention]
However, when the molded body has a curved portion or a bent portion, it is difficult to provide a cured layer with a uniform thickness. As a result, the surface of the molded body varies in scratch resistance and antifouling properties. Sometimes occurred. In addition, it is necessary to select a soft resin material having good adhesion to the cured layer, or there may be an additive or the like that inhibits the formation of the cured layer in the soft resin material. There is also a problem that is limited. Further, the coating process has a problem that it is complicated in the manufacturing process.
[0006]
Therefore, an object of the present invention is to provide a soft resin material molded body having a surface excellent in scratch resistance and antifouling property for a long period of time while maintaining the soft texture of the soft resin material.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies to solve the above problems. As a result, by laminating a thermoplastic resin film in which a protective layer made of a low surface energy substance is previously formed on the surface of the soft resin material so that the protective layer becomes the outermost layer, the soft resin material in the soft resin material molded body The adhesive layer, the curability and the like of the protective layer can be selected without limitation, and a layer made of a low surface energy substance can be stably formed on the surface of the soft resin material molded body, The present invention has been completed.
[0008]
  That is, the present invention has one surfaceHardened silicone resinA thermoplastic resin film made of an α-olefin-based resin having a protective layer formed of the α-olefin-based soft resin with the protective layer as the outermost layer.The durometer hardness (JIS K6253) is 30 to 70It is a soft resin material composite molded body characterized by being laminated by heat fusion to a molded body made of a soft resin material.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
  In the present invention, it is formed as a protective layer on one surface of the thermoplastic resin film.Silicone resin cured body (hereinafter referred to as “low surface energy substance”)Can be obtained by curing a treatment agent mainly composed of silicone resin such as polydimethylsiloxane and polymethylphenylsiloxane.ThingsIs mentioned.
[0010]
Among them, a product obtained by curing a treatment agent mainly composed of a silicone resin is more preferable because it is excellent in processability, adhesion to a thermoplastic resin film, and cost. If a specific treatment agent based on the silicone resin is specifically shown, it is directly bonded to the silicon atom of the reactive dialkylsiloxane having a plurality of carbon-carbon double bonds at the terminal or main chain of the dialkylsiloxane. Examples thereof include a silicone resin treatment agent having a composition in which a reactive siloxane derivative having one or more structures bonded with hydrogen atoms, a polymerization catalyst, and a polymerization regulator or a release regulator as necessary are added.
[0011]
Among the above-mentioned treatment agents, those having at least one alkylsiloxane having at least one carbon-carbon double bond as a main component are particularly preferred, and moreover, at least a carbon-carbon double bond in a solvent type or a solvent-free type having different molecular weights. The treatment using a mixture of alkyl siloxanes having one or more has high adhesion between the protective layer and the thermoplastic resin film, and the protective layer does not fall off during and after the lamination of the soft resin material molded body, and is uniform. Better scratch resistance and antifouling properties can be imparted to the structure, which is more preferable.
[0012]
In the present invention, the thickness of the protective layer made of a low surface energy material formed on one surface of the thermoplastic resin film is not particularly limited, but if it is too thick, it is economically disadvantageous or curable. When the treatment agent is used, curing may be insufficient, and if it is too thin, scratch resistance, antifouling property and the like are deteriorated. Therefore, the thickness of the layer made of the low surface energy substance is preferably in the range of 0.1 to 10 μm.
[0013]
Moreover, in this invention, as a method of forming the protective layer which consists of the said low surface energy substance on the surface of the said thermoplastic resin film, a well-known method is employ | adopted suitably according to the kind of said low surface energy substance.
[0014]
For example, when a low surface energy substance is obtained by curing a curable processing agent, a method of coating and curing the treatment agent on the surface of a thermoplastic oil-fat film, and a low surface energy substance can be formed. If the low surface energy substance can take the form of an oligomer having a molecular weight of about several hundred to several thousand, the method of forming it into a film and laminating it on the thermoplastic resin film can be applied to the surface of the thermoplastic resin film. The method of apply | coating and hardening further as needed is employ | adopted.
[0015]
In the above embodiment, when a treating agent is used, the treating agent can be either a solvent type diluted with a solvent or a solventless type which is not diluted with a solvent at all.
[0016]
In addition, as a method for applying the treatment agent to the thermoplastic resin film, conventionally used coating methods such as coating based on transfer methods such as gravure, gravure reverse, offset, bar, comma bar, etc. It is possible to employ coating based on a scraping method using the like, and a protective layer having a uniform thickness can be formed by these methods.
[0017]
  Furthermore, the curing of the treatment agent isMade of α-olefin resinA method is generally performed by irradiating heat, ultraviolet rays, or an electron beam after coating the surface of the thermoplastic resin film with a predetermined thickness. The above used in the present inventionMade of α-olefin resinAs a material of the thermoplastic resin film, a protective layer made of a low surface energy material such as the above-mentioned silicone resin can be formed on one surface thereof with a sufficiently cured state and adhesiveness, and the other surface is a soft resin. If it can be laminated on the material surface,Made of α-olefin resinA thermoplastic resin can be used without any limitation.
[0018]
  For example, homopolymer or copolymer made of α-olefin such as ethylene, propylene, buteneBody etc.These may be used alone or in admixture of two or more resins.
[0019]
SoftWhen the thermoplastic resin material molded body is made of an α-olefin-based soft resin and the thermoplastic resin film is laminated by thermal fusion, a thermoplastic resin film made of an α-olefin-based resin is suitable in terms of fusion strength. is there. In addition, in this invention, a film does not have a strict meaning with respect to thickness, but includes a sheet | seat and a molded object. Although the thickness of the thermoplastic resin film used in the present invention is not limited, when considering the soft texture and scratch resistance of the surface of the soft resin material composite molded body, the thickness is preferably 10 μm to 200 μm, and more preferably 30 μm to 120 μm. Those are more preferred.
[0020]
In the present invention, various additives are appropriately added to the thermoplastic resin constituting the thermoplastic resin film as long as it does not adversely affect the formation of a protective layer made of a low surface energy substance formed on one surface of the thermoplastic resin. Can be blended.
[0021]
Specifically, nucleating agents such as Al-pt-butylbenzoate and 2,2′-methylene-bis (4,6-di-tert-butylphenyl) phosphate metal salt; phenolic and organic phosphite , Antioxidants such as organic phosphorus such as phosnite and thioethers; heat stabilizers such as hindered amines; UV absorbers such as benzophenones, benzotriazoles, and benzoates; nonionics, cationics, anions, etc. Antistatic agents; Dispersants such as bisamides, waxes, and organometallic salts; Chlorine supplements such as carboxylates and hydrotalcite of alkaline earth metal salts; Amides, waxes, and organometallic salts Degrading agents such as oxides and hydrotalcites; Metal deactivators such as hydrazines and amines; Bromine-containing organics, phosphates, and trioxides Flame retardants such as antimony, magnesium hydroxide and red phosphorus; organic pigments; inorganic pigments; foaming agents; organic fillers; inorganic and organic antibacterial agents such as metal ions; talc, wollastonite, barium sulfate, calcium carbonate, Examples include inorganic fillers such as glass.
[0022]
In addition, when the formation of a protective layer made of a low surface energy substance involves a curing reaction using a catalyst, among the additives, nucleating agents such as metal phosphates; organic phosphites and organic phosphorus such as phosnite. -Based, thioether-based antioxidants; cationic-based, anionic-based antistatic agents; organometallic salt-based dispersants; organometallic salt-based lubricants; bromine-containing organic systems, phosphoric acid systems, antimony trioxide, Flame retardants such as magnesium hydroxide and red phosphorus; It is desirable to reduce as much as possible additives containing substances that inhibit the curing reaction such as metal ion systems, and their total abundance constitutes the thermoplastic resin film It is preferably 0.05 parts by weight or less, particularly 0.01 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin.
[0023]
The thermoplastic resin film may have a single layer structure or a multilayer structure in which a plurality of resins are combined. For example, when a thermoplastic resin film is laminated to a soft resin material molded body by heat fusion, the soft resin material surface layer portion has an affinity for the laminated surface with the soft resin material molded body in order to improve adhesion. Those obtained by selecting and laminating a good thermoplastic resin layer are preferred.
Further, the thermoplastic resin film may be a stretched film or an unstretched film, but the lamination of the thermoplastic resin film on the soft resin material molded body is performed by in-mold molding (in-mold molding). When performing, it is preferable to use an unstretched film from the surface of the followability to the shape in a metal mold | die of a thermoplastic resin film.
[0024]
On the other hand, when the obtained composite molded body places importance on surface gloss, it is preferable to use a stretched film. In this case, even in the case of a stretched film, the stretched film has a low stretch ratio, specifically, the area ratio is 10 If a thing of -30 times is used, it can be used conveniently without a problem about the followability of the shape in a metal mold | die.
[0025]
As a method for forming the thermoplastic resin film, known methods such as a casting method, a biaxial stretching method, and inflation can be used depending on the purpose.
[0026]
In the present invention, the thermoplastic resin film that has been subjected to secondary processing such as printing, metal laminating, vapor deposition or the like can be used as long as the effects of the present invention are not impaired. For example, it is recommended that the film is multilayered and the intermediate processing is performed on the intermediate layer.
Furthermore, in order to improve the adhesion with the protective layer, it is preferable to subject the surface on which the protective layer of the thermoplastic resin film is formed to surface treatment such as corona treatment and frame treatment in advance before forming the protective layer. .
[0027]
The greatest feature of the soft resin material composite molded body of the present invention is that the thermoplastic resin film on which the protective layer is formed is laminated on the surface of the soft resin material molded body with the protective layer as the outermost layer.
[0028]
That is, with this configuration, even when a curing reaction using a catalyst is involved in the formation of a protective layer made of a low surface energy substance, it is sufficiently cured without being affected by the shape and material of the soft resin material molded body, In addition, a protective layer having a uniform thickness can be formed on the surface of the soft resin material molded body with good adhesion.
[0029]
  In the present invention,Made of α-olefin soft resinThe kind and resin composition of the soft resin material constituting the soft resin material molded body can be arbitrarily selected according to the target characteristics. For example, as a soft resin material,Made of α-olefin soft resinSynthetic rubberUsedCan be used, but a durometer hardness (JIS K6253) of 30 to 70 is used..It is preferable from the point of soft feeling and moldability.
[0030]
Examples of the soft resin material include butadiene rubber, styrene-butadiene rubber, chloropyrene rubber, butadiene-acrylonitrile rubber, isobutylene-isoprene rubber, ethylene-propylene rubber, and thermoplastic elastomer. In particular, the use of ethylene-propylene rubber and thermoplastic elastomer as the soft resin material of the soft resin material molded body is favorable in terms of adhesiveness to the α-olefin film preferably used in the present invention and recyclability. .
[0031]
Further, when a thermoplastic resin film having a protective layer is laminated on the surface of a soft resin material molded body with the protective layer as the outermost layer, compression set (JIS K6301) is used as the soft resin material constituting the soft resin material molded body. , 23 ° C.−22 hr) is 30 or less, preferably 10 to 25 because it is difficult for wrinkles to occur in the thermoplastic resin film laminated thereon.
[0032]
In addition, you may mix and use other resin for the said soft resin material which comprises a soft resin material molded object in the range which does not impair the effect of this invention remarkably.
In the present invention, the shape of the soft resin material molded body can be any shape depending on various uses and functions. For example, in addition to a molded product having a uniform thickness such as a film, a deformed film having a changed thickness, a plate shape, a rod shape, and other arbitrary structures can be used.
[0033]
Moreover, you may make the shape of a soft resin material molded object into a hollow body according to various uses and functions. In this case, as a method for forming the hollow portion inside the molded body, a technique by gas injection may be used.
[0034]
Further, the soft resin material molded body can be provided with an insert made of metal or hard resin as a reinforcing agent.
[0035]
The soft resin material molded body preferably has a thickness of 0.5 mm or more even in the thinnest portion in consideration of the soft texture of the surface.
[0036]
In addition, as the soft resin material molded body, a material obtained by foaming a soft resin material at an arbitrary magnification can be used, and in this case, the soft texture can be further improved. In general, the foam has a poor surface state and poor design, but in the present invention, the surface appearance is very good by laminating a thermoplastic resin film on the foam.
[0037]
The soft resin material composite molded body of the present invention comprises a thermoplastic resin film in which a layer made of a low surface energy substance is formed on the one surface, and a protective layer as an outermost layer, on a part or the entire surface of the soft resin material molded body. It is configured by stacking.
[0038]
As the lamination mode, a known method is adopted according to the shape, material, etc. of the soft resin material molded body. For example, lamination by fusion, lamination via an adhesive layer, and the like can be mentioned. Lamination by fusion is preferable in terms of durability in adhesion between the soft resin material molded body and the thermoplastic resin fill.
[0039]
As a method of laminating by fusion, for example, in-mold molding (in-mold molding), insert molding, heat sealing, extrusion lamination, stampable molding, stamping molding, blow molding, etc. The method of doing is mentioned.
[0040]
The soft resin material composite molded body of the present invention preferably has a durometer hardness (JIS K6253) measured from the protective layer side of 30 to 80 in consideration of the soft feeling, and more preferably 40 to 70 Is more preferable.
[0041]
The present invention also provides a novel composite structure utilizing the soft feeling of the molded body by providing the molded body of the soft resin material as a surface layer of the hard material structure.
[0042]
That is, the present invention relates to a soft resin material composite in which a thermoplastic resin film in which a protective layer made of a low surface energy substance is formed on one surface is laminated on a molded body made of a soft resin material with the protective layer as an outermost layer. Provided is a composite structure in which a molded body is laminated on the surface of a structure made of a hard material (hereinafter also referred to as a hard material structure) with a protective layer as an outermost layer.
[0043]
The hard material can be used without any public restrictions such as various metals, ceramics, wood, thermoplastic resin, thermosetting resin, etc. The thermoplastic resin is polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS resin. , Methacrylic resins, polyamides, polycarbonates, polyacetals, polyester resins, cellulosic plastics, and the like, and thermosetting resins include epoxy resins, unsaturated polyester resins, phenol resins, and urea / melamine resins. In particular, when the adhesiveness with the soft resin is required for the function of the structure, it is preferable to use olefins, for example, when the soft resin is ethylene-propylene rubber or an olefinic thermoplastic elastomer, It is most effective to use one kind or two or more kinds of α-olefin homopolymers and copolymers such as ethylene, propylene, and butene-1 as the hard material.
[0044]
That is, by using a hard material having high adhesiveness with a thermoplastic resin film as described above, it is possible to exert a remarkable improvement effect on the scratch resistance as well as the antifouling property.
[0045]
In the present invention, the shape of the hard material structure is appropriately determined according to the shape required in various applications. For example, in the use as a refrigerator door, a housing for home appliances, a handle of an automobile, and an interior material, a plate-like body in which a bent portion is formed as necessary is common.
[0046]
In the composite structure of the present invention, it is preferable to use one having a durometer hardness (JIS K6253) measured from the protective layer side of 35 to 90 in consideration of softness, and more preferably 45 to 80. preferable.
[0047]
In the composite structure of the present invention, the soft resin material can be formed on a part or the entire surface of the hard material depending on the application to be used.
[0048]
Furthermore, when all of the composite structure of the present invention is composed of an olefin-based material, when the composite structure is crashed and reused, since the decrease in physical properties is small, the recycle compatibility becomes very high, preferable.
[0049]
In the present invention, as a method of laminating the soft resin material and the hard material, a known method can be used without limitation. For example, when a thermoplastic resin is used as the hard material, the soft resin is obtained by a two-head injection molding machine. There is a method in which after the material is primary molded, the hard material is secondarily molded and the both are integrally molded. In this case, examples of the mold structure include a core back method, a core rotation method, and a core slide method.
[0050]
A typical embodiment of the soft resin material composite molded article of the present invention is shown in FIG. As shown in FIG. 1, the molded article of the present invention basically comprises a thermoplastic resin film 2 in which a protective layer 3 is formed on a soft resin material molded article 1 and is laminated with the protective layer 3 as the outermost layer. Is done. Another embodiment is shown in FIG. As shown in FIG. 2, a thermoplastic resin film 2 in which a protective layer 3 is formed on a soft resin material layer 1 of a structure composed of a soft resin material layer 1 and a hard material 4 is laminated with the protective layer 3 as an outermost layer. Configured.
[0051]
【The invention's effect】
As can be understood from the above description, the soft resin material composite molded body of the present invention has a protective layer that is sufficiently cured and has a uniform thickness without being affected by the resin composition of the soft resin material molded body. Because it can be laminated on the surface of the soft resin material molded body with good adhesion, the surface has excellent scratch resistance and antifouling properties, and exhibits excellent characteristics such as soft touch feeling and shock absorption of the soft resin material molded body. can do.
[0052]
Therefore, characteristics such as a soft touch feeling and shock absorption of the molded body of the soft resin material are required in addition to the scratch resistance and antifouling property of the surface, for example, toilet lid, toilet seat, exterior of jar pot, vacuum cleaner Body, washing machine skin, personal computer and mobile phone housing, automotive interior parts such as pillars, trims, console boxes, and handles, vanity and kitchen door door handles, desk drawer fronts, chairs It can be suitably applied to uses such as armrests, chest corners, toys and the like.
[0053]
【Example】
EXAMPLES Hereinafter, examples will be shown to describe the present invention more specifically, but the present invention is not limited to these examples.
[0054]
In the following examples, physical properties were evaluated according to the following methods.
[0055]
(1) Adhesion between protective layer and thermoplastic resin film
The thermoplastic resin film or soft resin material molded body on which the protective layer is formed is allowed to stand in a constant temperature bath at 40 ° C. and a humidity of 90% for 24 hours, and then the protective layer is rubbed with a finger to remove the protective layer. It was observed visually. The surface condition was visually evaluated in the following three stages.
[0056]
○: Hardened and no dropout is observed.
[0057]
(Triangle | delta): Although it hardens | cures, adhesion is bad and omission is observed.
[0058]
X: It is not hardened and a haze (smear) is observed.
[0059]
(2) Adhesiveness between thermoplastic resin film and soft resin material
A test piece of 127 mm × 12.7 mm × 3 mmt is cut out from a soft resin material composite molded body in which a thermoplastic resin film as shown in FIG. 1 is formed by injection molding, and the thermoplastic resin film and the soft material are cut at the ends. The interface with the resin material molded body is partly forcibly peeled off, and each peeled part is pulled in the opposite direction with a tensile tester (5 ton autograph made by Shimadzu Corporation). evaluated.
[0060]
○: Adhesion is sufficient and cohesive peeling is observed.
[0061]
(Triangle | delta): It has not adhere | attached completely but partial aggregation peeling is observed.
[0062]
X: Almost no adhesion and interfacial peeling is observed.
[0063]
(3) Pencil hardness measurement
Measurement was performed according to JIS K5400.
[0064]
(4) Scratch test-a
The molded body was fixed to a fully automatic crosscut peel tester manufactured by Yasuda Seiki Seisakusho, a load of 100 g was applied with a diamond needle (R = 250 μm) standing upright on the surface of the molded body, and the test piece was 10 mm / sec. Slide at speed.
[0065]
After the test was completed, the difference between the highest point and the lowest point of the scar was measured with a laser microscope [1LM21] manufactured by Lasertec Co., Ltd. to obtain the maximum scratch depth (μm).
[0066]
(5) Scratch test-b
The molded body is fixed to a fully automatic crosscut peel tester manufactured by Yasuda Seiki Seisakusho, and toilet paper is laminated on a 2 cm square metal pad and brought into contact with the surface of the molded body. 100 g / cm²The test was conducted by reciprocating the molded body 100 times at a speed of 10 mm / sec at a pressure of 10 mm / sec. After completion of the test, the surface state of the molded body was visually evaluated in the following four stages.
[0067]
A: When the surface of the molded body is hardly noticeable
○: When the surface of the molded body is somewhat noticeable
Δ: When the surface of the molded body is noticeable
×: When the scratch on the surface of the molded product is noticeable
(6) Contamination resistance test
The area of 6mm width and 15mm length is painted on the surface of the molded body with oil-based magic (ARTLINE6mm black, manufactured by Shachihata Co., Ltd.). A cotton cloth laminated on a 2 cm square metal pad is brought into contact with 500 g / cm²The compact was reciprocated 100 times at a speed of 10 mm / sec with a pressure of 10 mm / sec. Thereafter, the ratio (area%) of the area where the ink remained on the molded body with respect to the coated surface was measured using an image analyzer (Pierce).
[0068]
(7) Durometer hardness
Measurement was performed from the protective layer side in accordance with JIS K6253 using a soft resin material composite molded body formed by injection molding and laminated with a thermoplastic resin film as shown in FIG.
[0069]
Example 1
(Creation of thermoplastic resin film)
(1) Adjustment of film raw materials
Melt flow rate 7.0 g / 10 min. 100 parts by weight of a propylene homopolymer (homopolypropylene), 100 parts by weight of the propylene homopolymer, 0.1 parts by weight of 2,6-di-t-butylhydroxytoluene as an antioxidant, and a chlorine scavenger The resin composition to which 0.1 part by weight of calcium stearate was added was mixed and stirred for 5 minutes with a Henschel mixer, and then granulated at 230 ° C. using an extrusion granulator having a diameter of 60 mm to obtain a raw material A.
[0070]
(2) Creation of film
A thermoplastic resin film was prepared using the raw material A by the following method.
[0071]
The raw material A was supplied to an extruder having a screw diameter of 75 mm, extruded from a T die at a resin temperature of 230 ° C., and a substantially unstretched single layer film having a thickness of 60 μm was obtained through a 30 ° C. cooling roll. Subsequently, a corona discharge treatment was performed so that the wetness index of one surface was 40 mN / m, and then aging was performed at 40 ° C. for 24 hours to obtain a thermoplastic resin film.
[0072]
(3) Formation of protective layer
LTC760A as solvent-type silicone: solid content concentration 30% (Toray Dow Corning Silicone) 20.32g, SRX212 (Toray Dow Corning Silicone) 0.19g as a curing catalyst, SD7200 (Toray) as a polymerization regulator -0.08g made by Dow Corning Silicone) and 67.85g heptane as a diluent solvent were mixed and stirred. This solution is designated as Silicone Solution X. 10.10 g of LTC1055 (manufactured by Toray Dow Corning Silicone) as solvent-free silicone and 1.0 g of LTC1102 (manufactured by Toray Dow Corning Silicone) as a curing catalyst were mixed and stirred. This solution is designated as Silicone Solution Y. 15 g of silicone solution X and 0.5 g of silicone solution Y were mixed to obtain a uniform solution. The mixed solution was applied to the corona-treated surface side of the thermoplastic resin film using a Mayer bar applicator (No. 5). Thereafter, the solvent was removed with a cool dryer. Subsequently, a thermoplastic resin film having a protective layer formed on one surface was obtained by curing with a 120 ° C. hot air circulation dryer.
(Creation of composite molded body: creation of soft resin material molded body and lamination of thermoplastic resin film)
After holding the thermoplastic resin film (100 mm × 100 mm) having a protective layer made of a silicone resin on one surface created by the above method in the injection mold in such a manner that the protective layer of the film is in contact with the mold, Olefin-based thermoplastic elastomer [Mitsui Petrochemical Industries, Ltd .: 5030N MFR (230 ° C./10 kg) = 50 g / 10 min, durometer hardness (JIS A) = 50, compression set (JIS K6301 / 23 ° C.−22 hr) = 22] was injection molded at a resin temperature of 230 ° C. and a mold temperature of 40 ° C. to produce a composite molded body (50 mm × 800 mm × 4 mmt) on which a thermoplastic resin film was laminated. (The unnecessary thermoplastic resin film part was trim-cut.) The thickness of each layer was 5 μm for the protective layer, 60 μm for the thermoplastic resin film, and about 4 mmt for the molded body of the soft resin material. An evaluation test was performed using the obtained composite molded body. The results are shown in Table 1.
[0073]
Examples 2-3
In Example 1, tris (2,4-t-butylphenyl) phosphite, which is a phosphorus-based antioxidant, and a phenol-based antioxidant, tetrakis [methylene-3- (3,5-di-), are used as film materials in Example 1. t-butyl-4-hydroxydiphenyl) propionate] The same procedure as in Example 1 except that a predetermined amount of methane was added. The amounts added and the results are shown in Table 1.
Example 4
A soft resin material composite molded body was produced in the same manner as in Example 1 except that a substantially unstretched thermoplastic resin film having a thickness of 300 μm was prepared in Example 1. The thickness of each layer was 5 μm for the protective layer, 300 μm for the thermoplastic resin film, and about 3.7 mmt for the molded body of the soft resin material. An evaluation test was performed using the obtained composite molded body. The results are shown in Table 1.
[0074]
  Example 5
  In a core slide type injection mold, a thermoplastic resin film (100 mm × 100 mm) having a protective layer made of a silicone resin formed on one surface formed in Example 1 is in contact with the mold. Olefin-based thermoplastic elastomer [Mitsui Petrochemical Industries, Ltd .: 5030N MFR (230 ° C./10 kg) = 50 g / 10 minutes, durometer hardness (JIS A) = 50, compression set (JIS K6301 / 23 ° C.−22 hr) = 22] was first molded at a resin temperature of 230 ° C. and a mold temperature of 40 ° C. with a two-head injection molding machine (manufactured by Nippon Steel Works: J150EII-2M), After securing the secondary material filling space by sliding the core in the mold, propylene homopolymer (manufactured by Tokuyama Corporation: SH152 MFR = 16 g 10 minutes) the same resin temperature 230 ° C., a mold temperature of 40 ° C., was prepared thermoplastic resin film is laminated composite structure of (50mm × 800mm × 4mmt). (The unnecessary thermoplastic resin film part was trim-cut.) The thickness of each layer was 5 μm for the protective layer, 60 μm for the thermoplastic resin film, about 2 mmt for the soft resin material layer, and about 2 mmt for the hard material. An evaluation test was performed using the obtained composite structure. The results are shown in Table 1.
  Comparative Example 1
  In Example 1, a styrene-based thermoplastic elastomer [manufactured by Shell Japan Co., Ltd .: D-4270 MFR (200 ° C./5 kg) = 15 g / 10 min, durometer hardness (JIS A) = 46, compression set ( JIS K6301 / 23 ° C.−22 hr) = 25] was used, and the same procedure as in Example 1 was performed. The results are shown in Table 1.
  Example6
  In Example 1, an olefinic thermoplastic elastomer [manufactured by Tokuyama Corporation: M142E MFR (230 ° C./2.16 kg) = 10 g / 10 minutes, durometer hardness (JIS A) = 58, compression set (JIS) K6301 / 23 ° C.−22 hr) = 40] was used in the same manner as in Example 1. The results are shown in Table 1.
[0075]
  Comparative example2
  The same operation as in Example 1 was conducted except that the thermoplastic resin film subjected to the protective treatment in Example 1 was not laminated. The results are shown in Table 1.
[0076]
  Comparative example3
  Example 1 was performed in the same manner as Example 1 except that a thermoplastic resin film having no protective layer was used. The results are shown in Table 1.
[0078]
[Table 1]

[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view of the present invention in which a thermoplastic resin film in which a protective layer made of a low surface energy substance is formed on one surface is laminated on the surface of a soft resin material molded body so that the protective layer is the outermost layer. It is a figure which shows the typical shape of a resin material composite molded object.
FIG. 2 is a diagram showing a typical shape of a composite structure in which a soft resin material composite molded body is laminated on the surface of a structure made of a hard material with a protective layer as an outermost layer in the present invention.
[Explanation of symbols]
1 Soft resin material molding
2 Thermoplastic resin film
3 Protective layer
4 Hard materials

Claims (4)

Thermoplastic resin film consisting of one to form a protective layer made of a silicone resin cured product on the surface alpha-olefin resin, the protective layer as an outermost layer, alpha-olefin soft resin from Do Ri durometer ( A soft resin material composite molded body, wherein JIS K6253) is laminated by heat fusion to a molded body made of a soft resin material of 30 to 70 . The protective layer made of a cured silicone resin is a cured silicone resin formed by a curing reaction using a catalyst, and the thermoplastic resin film made of an α-olefin resin contains an antioxidant, 2. The content of the organic phosphorus-based and thioether-based antioxidant in the antioxidant is 0.01 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin constituting the thermoplastic resin film. Soft resin material composite molded body.   A composite structure in which the soft resin material composite molded body according to claim 1 or 2 is laminated on a surface of a structure made of a hard material with a protective layer as an outermost layer. A protective layer made of a silicone resin cured body is formed on one surface of a thermoplastic resin film made of an α-olefin resin, and then the α-olefin soft resin is placed so that the protective layer side is the outer layer side. Do a resin Ri durometer hardness (JIS K6253) is laminated by thermal fusion the molded body made of a soft resin material 30 to 70, the manufacturing method of the soft resin material composite molded article according to claim 1 or 2.

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