JPH10306192A - Film and molded item prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film or sheet excellent in thickness accuracy by using a compsn. which contains an acrylic polymer having a specified viscosity and a multilayered acrylic polymer. SOLUTION: This film or sheet is formed from a compsn. comprising 20-90 pts.wt. acrylic polymer (A) having a reduced viscosity of 0.07 L/g or higher, 10-50 pts.wt. multilayered acrylic polymer (B) contg. a rubbery elastomeric layer, and 0-70 pts.wt. acrylic resin (C) having a reduced viscosity lower than 0.07 L/g, the sum of the three ingredients being 100 pts.wt. Pref., ingredient A comprises 10-90 wt.% methyl methacrylate units and 90-10 wt.% alkyl acrylate units. Ingredient B is pref. a three-layered polymer which comprises the innermost layer of a hard polymer formed mainly from methyl methacrylate, the intermediate layer of a soft rubbery elastomeric copolymer formed from a (4-8C)-alkyl acrylate and a polyfunctional monomer, and the outermost layer of a hard polymer similar to ingredient A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a film or sheet and a molded article using the same.

[0002]

2. Description of the Related Art The simultaneous lamination method of injection molding is disclosed in
As disclosed in JP-A-6339, JP-B-4-9647, JP-A-7-9484, etc., a film or sheet inserted between male and female molds during injection molding is injected into a cavity. This is a method of decorating or painting the surface of a molded body by integrating it with a resin, and is a molding method called a lamination method or a transfer printing method depending on the type of film used.

Conventionally, an acrylic film or an acrylic sheet has been known as a film or sheet used in such a simultaneous injection molding laminating method, but its thickness accuracy has not been said to be sufficient.

[0004]

The inventors of the present invention have conducted intensive studies to develop a film or sheet having a sufficient thickness accuracy. As a result, an acrylic polymer having a specific reduced viscosity and an acrylic polymer having a multilayer structure have been obtained. It has been found that a film made of a resin composition containing the following is excellent in thickness accuracy, and has led to the present invention.

[0005]

That is, the present invention provides:
(I) 20 to 90 parts by weight of an acrylic polymer having a reduced viscosity of 0.07 L / g or more, (II) 10 to 50 parts by weight of an acrylic polymer having a multilayer structure including a rubber elastic layer, and (II)
I) containing from 0 to 70 parts by weight of an acrylic resin having a reduced viscosity of less than 0.07 L / g, and (I), (II) and (I)
The present invention provides a film or sheet comprising a resin composition having a total amount of II) of 100 parts by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylic polymer (I) used for the film or sheet of the present invention (hereinafter collectively referred to as "film") has a reduced viscosity (0.1 g of the polymer and 100 ml of chloroform). Dissolved at 25 ° C
The value measured in. ) Needs to be 0.07 L / g or more. If it is less than 0.07 L / g, it becomes difficult to produce a film with good thickness accuracy because the melt tension at the time of film processing is reduced, and it is preferably 0.1 L / g or more. Further, the reduced viscosity is preferably 0.25 L / g or less, more preferably 0.2 L / g or less, from the viewpoint that a film can be easily produced.

As such an acrylic polymer, for example, an acrylic polymer comprising a methyl methacrylate unit and an alkyl acrylate unit is exemplified. The alkyl group in the alkyl acrylate is preferably an alkyl group having 2 to 10 carbon atoms. Examples of the alkyl acrylate include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-acrylate. -Butyl, isobutyl acrylate, hexyl acrylate, octyl acrylate and the like. The methyl methacrylate unit in the acrylic polymer is preferably 10 to 90% by weight, and the alkyl acrylate unit is preferably 90 to 10% by weight. The glass transition temperature of such an acrylic polymer is generally in the range of 40 to 100 ° C, but is in the range of 40 to 80 ° C.
Is preferably within the range.

[0008] The content of the acrylic polymer in the resin composition is 20 to 90 parts by weight. If the amount is less than 20 parts by weight, irregular appearance of the film tends to be easily generated on the film surface, and if the amount exceeds 90 parts by weight, a film having a low surface hardness tends to be obtained, which is not practically preferable.

(II) The acrylic polymer having a multilayer structure including a rubber elastic layer is an acrylic polymer having a multilayer structure of at least two layers, preferably three layers. The particle size of such an acrylic polymer is usually in the range of 100 to 500 nm. As the two-layer acrylic polymer, the inner layer is a soft rubber composed of a copolymer of an alkyl acrylate having an alkyl group having 4 to 8 carbon atoms and a polyfunctional monomer, and the outer layer is formed of methyl methacrylate. And those based on a two-layer structure which is a hard polymer mainly composed of Further, as the acrylic polymer having a three-layer structure, the innermost layer is a hard polymer containing methyl methacrylate as a main component, and the intermediate layer is an alkyl acrylate having an alkyl group having 4 to 8 carbon atoms and a polyfunctional monomer. A soft rubber elastic layer made of a copolymer of a monomer and a three-layer structure whose outermost layer is made of a hard polymer mainly composed of methyl methacrylate are exemplified. Above all, 20-60% by weight of rubber elastic layer
Those containing are more preferred. Such an acrylic polymer having a multilayer structure is described in, for example, Japanese Patent Publication No. 55-27576, Japanese Patent Application Laid-Open No. 1-252653, and the like. The content of the multi-layer acrylic polymer needs to be 10 to 50 parts by weight. If the amount is less than 10 parts by weight, the impact strength tends to be insufficient or the film elongation required for the laminated composite in the mold tends not to be obtained. If it exceeds 50 parts by weight, the surface hardness of the film tends to decrease, which is not preferable.

The film of the present invention comprises a resin composition containing the above acrylic polymer and a multilayer acrylic polymer containing a rubber elastic layer, and (III) an acrylic resin having a reduced viscosity of less than 0.07 L / g. The content of the acrylic resin may be 0, that is, it may not be contained, but the acrylic resin (III) may be contained in an amount of 0 to 70 parts by weight, and in this case, a film having more excellent heat resistance is obtained. It is preferable in that it can be obtained. As such an acrylic resin, for example, methyl methacrylate unit of 50% by weight or more,
Those comprising less than 50% by weight of one or more other vinyl monomer units copolymerizable therewith are exemplified.

The vinyl monomers copolymerizable with methyl methacrylate include, for example, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid. Methacrylates such as 2-hydroxyethyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and the like Acrylic esters,
Examples include unsaturated fatty acids such as acrylic acid and methacrylic acid, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, and cyclohexylmaleimide. The glass transition temperature of such an acrylic resin is generally 80 ° C. or higher.

The reduced viscosity of such an acrylic resin is usually at least 0.03 L / g, preferably from 0.03 to 0.1.
065 L / g.

(III) When an acrylic resin having a reduced viscosity of less than 0.07 L / g is used, its content is usually at least 10 parts by weight. On the other hand, when the content exceeds 70 parts by weight, irregularities tend to be easily generated on the surface of the film.

In the film of the present invention, (I) an acrylic polymer having a reduced viscosity of 0.07 L / g or more;
In the content of (II) an acrylic polymer having a multilayer structure containing a rubber elastic layer and (III) an acrylic resin having a reduced viscosity of less than 0.07 L / g, the sum of (I), (II) and (III) The amount is 100 parts by weight.

The resin composition of the present invention may contain usual additives. Such additives include, for example, hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, ultraviolet absorbers, weathering agents such as hindered amine light stabilizers, flame retardants, colorants, pigments, inorganics And the like. As an ultraviolet absorber,
Generally, a benzotriazole-based or benzophenone-based ultraviolet absorber is used alone or in combination, but from the viewpoint of reducing volatilization from a film and preventing deterioration of a printed pattern, a benzotriazole-based or benzophenone-based ultraviolet absorber is used. Triazole UV absorbers are preferred.

In order to produce such a resin composition, for example, (I) an acrylic polymer and (II) a multilayer acrylic polymer containing a rubber elastic layer, or further (III)
The acrylic resin may be mixed by a method such as melt kneading using an extruder or the like.

The film of the present invention can be obtained from such a resin composition by an extrusion casting method using a well-known chill roll, an extrusion molding method in which both sides of the film are brought into contact with the roll surface, and both sides in contact with a metal belt. It can be manufactured by a belt cooling extrusion method, an inflation extrusion molding method, a solvent casting method, or the like. Among them, the extrusion molding method in which both surfaces of the film are brought into contact with a roll surface or a metal belt, the method of manufacturing by a belt cooling extrusion method, etc., not only can obtain a film having a good surface condition, but also reduce the external haze. It is also desirable from the viewpoint of the print-out prevention effect, which is the printing characteristic of the picture.

The film of the present invention may be used by printing a pattern or the like on one side, or may be used by being colored. Further, a film obtained by giving a shape by thermoforming such as vacuum forming in advance may be used for simultaneous lamination with injection molding. Further, the film of the present invention may be used as the outermost layer of a multilayer film. That is, the film of the present invention can be made into a multilayer film by backing another resin film such as a vinyl chloride film or a transparent ABS film.

The thickness of the film of the present invention is 0.1 to 0.6.
mm. The film of the present invention is usually supplied in a state in which a pattern or the like is printed on one side, and the printed surface is directed toward the resin side to be melt-injected after the injection mold. In other words, this is because the purpose is to increase the printing depth of the transparent (clear) layer in the state of the final molded product. Therefore, if the thickness of the film is less than 0.1 mm, the sense of depth of a printed pattern or the like becomes poor, which is not preferable. In addition, in order to industrially carry out the simultaneous lamination of the injection molding of the present invention in a mold, it is preferable to continuously supply the film into the mold. For this purpose, the thickness of the film is preferably 0.6 mm or less, but if it exceeds 0.6 mm, it tends to be difficult to wind in a continuous roll, which is not preferable.

As described above, for example, an ABS resin, a polycarbonate resin, a polystyrene resin or a polyolefin resin can be used as the resin which is melt-injected into a mold at the time of simultaneous lamination of the film of the present invention during injection molding. ,
It is desirable to select an ABS resin or a polycarbonate resin from the viewpoints of impact resistance, dimensional stability, and the like of the finished product. Further, in the case where the film is continuously supplied as industrial production, a film thickness of 0.1 to 0.2 mm is preferable from the viewpoints of reduction in winding weight and moldability during vacuum forming. In the case of a film thickness exceeding 0.2 mm, it is advantageous to feed the film into the mold every leaf.

The simultaneous lamination by injection molding using the film of the present invention is disclosed in JP-B-63-6339 and JP-B-4-964.
No. 7, JP-A-7-9484 and the like. That is, open the female mold and the male mold that form the cavity space, insert the film between both molds, close both molds with the film in between, close the mold, and inject the molten resin into the cavity from the gate By filling and cooling and solidifying, a film is adhered and integrated on the surface of the injected molded body, and then both molds are opened to obtain a molded body. Conditions such as the resin temperature and the injection pressure of the injection molding are appropriately set in consideration of the type of the resin and the like.

The simultaneous lamination by injection molding using the film of the present invention takes advantage of the characteristics of the methacrylic resin such as weather resistance, surface hardness, and surface gloss, thereby making it possible to use a bumper, a garnish, a side panel such as an automobile outer panel member, or a center. It is useful as a method for producing paint replacements such as interior parts for automobiles such as consoles and door trims, and exterior parts for home appliances such as air conditioners and refrigerators.

Further, the film of the present invention can be used as a material for surface decoration technology such as gravure printing, screen printing or printing by an ink jet printer utilizing computer graphic technology, taking advantage of the feature of excellent surface smoothness. . The film printed in this way is provided with an adhesive layer on one side to be used as a display film (marking film) for exterior / advertisement, a surface decoration film for building materials such as kitchen outer plates and table outer plates, etc. Can be used. The adhesive layer in this case may be provided on the printing surface side, or may be provided on the opposite side of the printing surface,
It can be selected according to the display or decoration purpose. This marking film is printed with various characters, pictures, photographs, and the like, and can be used for decoration, guidance display, and the like of, for example, passenger cars, buses, railway vehicles (trains, passenger cars, and the like). In addition, the methacrylic resin is useful for outdoor signboards, window signboards, and the like by utilizing the excellent weather resistance of the methacrylic resin. Such a display film has better weather (light) resistance than conventional soft vinyl chloride resin films, polyurethane resin films, PET resin films, etc., which are the materials of marking films. When used as a building material decorative film, surface hardness and surface gloss, which are characteristics of methacrylic resin, can be significant advantages.

Further, the film of the present invention can be used as a masking film for the purpose of protecting a base material, taking advantage of its feature of being excellent in transparency. As a general masking film, a film in which a pressure-sensitive adhesive layer is attached to a polyethylene resin film is used. However, since the polyethylene resin is crystalline, it is translucent, and optical distortion is likely to occur. It has the drawback of saying. On the other hand, the masking film having an adhesive layer on one side of the present invention, when used as a masking film such as a methacrylic resin plate or a polycarbonate resin plate, is transparent, so that the product defect can be directly visually inspected without peeling off the masking film. Can be inspected. In addition, when used as a protective masking film such as a polarizing film or a retardation film, it is possible to directly perform a characteristic test such as optical distortion or detergence without removing the masking film.

[0025]

The film of the present invention is excellent as a film for simultaneous lamination or lamination for injection molding.
The use of this film makes it possible to easily and inexpensively produce a laminated molded product having a high surface hardness and a deep and transparent feeling. Further, it can be preferably used for a composite film, a marking film, and a masking film.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The evaluation method is as follows. (1) Irregularity generation test during molding: The surface state of the laminated synthetic body was visually observed, and the surface state was evaluated as good, the fine irregularity was evaluated as x, and the middle was evaluated as Δ. (2) Gauze abrasion: Gauze was attached to a measuring jig of a D-type friction tester for dyeing fastness manufactured by Toyo Seiki Seisaku-sho, Ltd., and a 500-reciprocal abrasion test was performed under a load of 200 g, and the evaluation was visually judged. .し な い indicates no wear, X indicates worn, and Δ indicates the middle. (3) Surface hardness: Pencil hardness was measured according to JIS K5400. (4) Transparency: Total light transmittance (Tt) and haze were measured according to the method described in JIS K 6718. (5) Glass transition temperature (Tg): Differential scanning calorimetry (D
SC), the endothermic onset temperature observed when the film sample was heated at a heating rate of 10 ° C./min was determined by the tangential method. (6) Number of missing prints: A picture was gravure-printed on one side of the film, a film having a width of about 1 m and a length of about 10 m was visually inspected, and the number of missing prints was converted per 1 m 2. (7) thickness precision: average thickness (d ₀₎ at a 1/1000 mm precision dial gauge for direction 1m take over a width direction thickness of the film, to measure the maximum section thickness and minimum unit thickness, the maximum thickness and d ₀ The thickness accuracy is calculated from the larger value (Δd) of the difference or the difference between the minimum thickness and d ₀ (d) and d ₀ by the following formula (1): thickness accuracy (%) = Δd / d ₀ × 100 (1) Was.

Example 1 Acrylic polymer (reduced viscosity 0.14 L / g, manufactured by bulk polymerization method, 85% by weight of methyl methacrylate unit,
60 parts by weight of a pellet of methyl acrylate units (15% by weight) and a spherical multi-layered acrylic polymer having a three-layer structure [the innermost layer is composed of 37.5 parts by weight of methyl methacrylate and 0.075 part by weight of diallyl maleate] A crosslinked polymer, the intermediate layer is a soft rubber elastic body composed of 38.5 parts by weight of butyl acrylate, 9 parts by weight of styrene, and 0.95 parts by weight of diallyl maleate; the outermost layer is 14.4 parts by weight of methyl methacrylate and Acrylic polymer consisting of a copolymer with 1.6 parts by weight (see Example 3 of Japanese Patent Publication No. 55-27576: average particle size: about 300 nm) and 24 parts by weight of an acrylic resin (Sumipex, manufactured by Sumitomo Chemical Co., Ltd.) LG, 16 parts by weight of beads having a reduced viscosity of 0.06 L / g) were mixed with a tumbler type mixer and melt-kneaded with a twin-screw extruder to form pellets. The pellets were prepared by using Toshiba Machine Co., Ltd.
Using a 5 mmφ single screw extruder, extrude through a T-die (600 mm width) at a set temperature of 255 ° C., cool so that both sides are completely in contact with the polishing roll, and have a thickness of 0.13 m.
m was obtained.

The obtained film having a thickness of 0.13 mm is
Put in the injection mold (temperature 50 ° C)
Inject S resin to 3mm thickness (injection pressure 1150kg /
cm ^Two, Resin temperature 230 ° C).
A shape (thickness: 3 mm) was obtained. The resulting film and component
Table 1 shows the evaluation results of the shapes.

Example 2 Acrylic polymer (produced by suspension polymerization, reduced viscosity 0.09 L / g, methyl methacrylate unit 87% by weight,
37.5 parts by weight of beads of methyl acrylate unit 3% by weight, butyl acrylate unit 10% by weight), 25 polymer parts of the same spherical three-layered multi-layer acrylic polymer used in Example 1, and Example 1 37.5 parts by weight of the same acrylic resin as used in 1) was mixed with a Henschel type mixer and melt-kneaded with a twin-screw extruder to form pellets.

The pellets were extruded through a T-die (600 mm width) at a set temperature of 255 ° C. using a single-screw extruder having a barrel diameter of 65 mm manufactured by Toshiba Machine Co., Ltd. Cool so that both sides of the film are completely in contact.
mm of film was obtained. Then, the obtained thickness 0.13
A molded product was obtained in the same manner as in Example 1 using a 1-mm-thick film. Table 1 shows the evaluation results of the obtained films and molded products.

Example 3 A film and a molded product were obtained in the same manner as in Example 2, except that the film was cooled by contacting only one side with a polishing roll. Table 1 shows the evaluation results.

Example 4 The amount of the acrylic polymer used in Example 2 was changed to 50 parts by weight, and the amount of the acrylic polymer having a three-layer structure was changed to 2 parts.
A film and a molded body were obtained in the same manner as in Example 2, except that the amount of the acrylic resin was 0 part by weight and the amount of the acrylic resin was 30 parts by weight. Table 1 shows the evaluation results.

Example 5 A multilayer acrylic polymer having a two-layer structure was used in place of the acrylic polymer having a three-layer structure [38.5 parts by weight of butyl acrylate, 9 parts by weight of styrene, and 0.1 part of diallyl maleate were used. 95 parts by weight of a soft rubber elastic body, the outer layer of which is 14.4 parts by weight of methyl methacrylate and 0.6 part of ethyl acrylate
Copolymer with parts by weight (produced without forming the innermost layer in accordance with Example 3 of JP-B-55-27576): average particle size is about 300 nm. Thus, a film was obtained to obtain a molded product. Table 1 shows the evaluation results.

Comparative Example 1 Instead of the acrylic polymer (reduced viscosity 0.09 L / g), an acrylic polymer (reduced viscosity 0.06 L / g, manufactured by a suspension method, 87% by weight of methyl methacrylate unit, Methyl acrylate unit 3% by weight, butyl acrylate unit 1
0% by weight) in the same manner as in Example 2, except that
A film and a molded product were obtained. Table 1 shows the evaluation results.

[0035]

[Table 1]

Claims (9)

[Claims] (1) 20 to 90 parts by weight of an acrylic polymer having a reduced viscosity of 0.07 L / g or more; (II) 10 to 50 parts by weight of an acrylic polymer having a multilayer structure containing a rubber elastic layer; III) containing from 0 to 70 parts by weight of an acrylic resin having a reduced viscosity of less than 0.07 L / g;
A film or sheet comprising a resin composition in which the total amount of I) and (III) is 100 parts by weight. 2. The film or sheet according to claim 1, wherein the acrylic polymer is an acrylic polymer comprising 10 to 90% by weight of methyl methacrylate units and 90 to 10% by weight of alkyl acrylate units. 3. A multilayer acrylic polymer having a rubber elastic layer, wherein the innermost layer is a hard polymer mainly composed of methyl methacrylate, and the intermediate layer is an alkyl acrylate having an alkyl group having 4 to 8 carbon atoms. 2. A three-layer acrylic polymer comprising a soft rubber elastic body composed of a copolymer of an ester and a polyfunctional monomer, and a hard polymer composed mainly of methyl methacrylate as an outermost layer. Film or sheet. 4. The method according to claim 1, wherein the thickness is 0.1 to 0.6 mm.
The film or sheet according to item 1. 5. The film or sheet according to claim 1, wherein a picture is printed on one side. 6. The film or sheet according to claim 1, which is formed by bringing both surfaces into contact with a roll surface or a metal belt surface. 7. A molded article obtained by bonding the film or sheet according to claim 1 or 5 to a surface layer of a thermoplastic resin molded article. 8. The molded article according to claim 7, wherein the thermoplastic resin is an acrylonitrile / butadiene / styrene resin or a polycarbonate resin. 9. The film or sheet according to claim 1 or 5 is inserted between male and female molds, and the film or sheet is simultaneously formed on the surface of a molded product obtained by injection molding a thermoplastic resin in the mold. The method for producing a molded article according to claim 7, wherein the molding is performed.