JP2000086853A - Acrylic resin film - Google Patents

Abstract

(57) [Problem] To provide an acrylic resin film that satisfies sufficient thickness accuracy, surface smoothness, and surface hardness at the same time. An acrylic resin having a glass transition temperature of 60 to 110 ° C. and a weight average molecular weight of 70,000 to 600,000.
An acrylic resin film comprising an acrylic resin composition containing 5 to 50 parts by weight and 5 to 50 parts by weight of a multilayer acrylic polymer having a rubber elastic layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin film and a laminated film thereof, and further to their uses.

[0002]

2. Description of the Related Art Conventionally, molded articles formed by injection molding have been used for interiors of automobiles, exteriors of home electric appliances, and the like. As a decoration of such a molded article, it is known that, for example, a resin film on which a decoration has been given is formed by a simultaneous injection molding laminating method, and simultaneously bonded to the molded article. Injection molding simultaneous lamination method is to place a film in advance between the male and female molds at the time of injection molding, inject the molten resin into the cavities of both molds, mold the molten resin, and simultaneously A method of laminating a film (for example, Japanese Patent Publication No. 63-6339,
This method is also called a lamination method, a transfer printing method, or the like depending on the type of film used. An acrylic resin film is known as a film used in the simultaneous lamination method of the injection molding, and for example, one side or both sides thereof is used after being printed with a design by printing.

Acrylic resin films are also used as films for covering the surface of, for example, polycarbonate resin sheets because of their excellent weather resistance (Japanese Patent Publication No. 47-19119, Japanese Patent Publication No. No. 55-59929).

However, conventional acrylic resin films have not been sufficiently satisfactory in terms of thickness accuracy, surface smoothness, surface hardness and the like.

[0005]

The inventors of the present invention have conducted intensive studies to develop an acrylic resin film which simultaneously satisfies sufficient thickness accuracy, surface smoothness, and surface hardness. Glass transition temperature of 7-6
An acrylic resin having a weight average molecular weight of 10,000,
A film made of an acrylic resin composition containing a multilayer acrylic polymer containing a rubber elastic layer and having sufficient thickness accuracy, surface smoothness, and surface hardness, and the acrylic resin film and the same The laminated film is suitable for various applications such as injection molding simultaneous bonding film, agricultural film, display film, masking film and paint substitute film, especially the film which is colored or printed with a pattern etc. The present invention has been found to be superior in the sense of depth when laminated and the printability of a picture, as compared with the acrylic film of the present invention, and reached the present invention.

[0006]

The present invention has a glass transition temperature of 60 to 110 ° C. and a weight average molecular weight of 70,000 to 60.
Provided is an acrylic resin film comprising an acrylic resin composition containing 95 to 50 parts by weight of an acrylic resin and 5 to 50 parts by weight of a multilayer acrylic polymer including a rubber elastic layer. Color this film,
Provided is a colored film that exhibits a sense of depth, metallic tone, and the like when laminated. A laminated film is provided by laminating a film such as a soft vinyl chloride film on the acrylic resin film. Further, the present invention provides a laminated molded product obtained by bonding these films to a molded product such as a polycarbonate resin. Further, the present invention provides applications of these films to agricultural films, display films, masking films, and coating substitute films.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The glass transition temperature of an acrylic resin is generally in the range of about 30.degree. C. to 110.degree.
And preferably about 75-105 ° C.
Range. The glass transition temperature is a value measured using a differential scanning calorimeter under a stream of N2 at a heating rate of 10 ° C./min. If the glass transition temperature is less than about 60 ° C., a film having a sufficient surface hardness tends to not be obtained. Acrylic resins having a glass transition temperature of about 110 ° C. or higher have a crosslinked structure and are difficult to mold. The glass transition temperature of the acrylic resin is generally in the range of about 30 ° C. to 110 ° C., but the acrylic resin used in the present invention has a glass transition temperature of 6 ° C.
It is necessary that the temperature be 0 ° C to 110 ° C.

The weight-average molecular weight needs to be about 70,000 to 600,000, preferably in the range of about 120,000 to 300,000. Such a weight average molecular weight can be measured by a method such as gel permeation chromatography (GPC). If the weight average molecular weight is less than about 70,000, the moldability when processing into a film is deteriorated, and sufficient thickness accuracy tends not to be obtained. If the weight-average molecular weight exceeds about 600,000, it becomes difficult to mold the film into a film, and gel-like foreign matter tends to be easily generated in the film.

Examples of the acrylic resin include polyalkyl methacrylate and a copolymer of alkyl methacrylate and alkyl acrylate. The alkyl methacrylate unit content in the copolymer of alkyl methacrylate and alkyl acrylate is about 50 to 99.
% By weight, and the content of the alkyl acrylate unit is about 50%.
It is preferably about 1% by weight.

The alkyl methacrylate includes, for example, methyl methacrylate. As the alkyl group in the alkyl acrylate, for example, two to two carbon atoms
10 alkyl groups are preferred, and specific examples of the alkyl acrylate include ethyl acrylate and n-acrylate.
Propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, octyl acrylate and the like.

The acrylic resin is manufactured by a known bulk polymerization method or suspension polymerization method. The glass transition temperature is adjusted depending on the amount and type of the comonomer used. The glass transition temperature generally increases as the amount of the comonomer decreases, and decreases as the molecular weight of the comonomer increases. The weight average molecular weight is adjusted by the type and amount of the polymerization initiator, the type and amount of the chain transfer agent, and the polymerization temperature.

The acrylic resin used in the present invention may be used as it is without mixing a polymer obtained by polymerization with another polymer, but is a mixture of resins having different glass transition temperatures or weight average molecular weights. You may. Even if the resin has a glass transition temperature or a weight average molecular weight different from about 60 to 110 ° C. or about 70,000 to 600,000, it is sufficient that a mixture thereof satisfies about 60 to 110 ° C. or about 70,000 to 600,000. .

Above all, a mixture containing at least one resin component having a weight average molecular weight of about 70,000 to 200,000 is preferable in view of the surface hardness of the film. Furthermore, when a mixture containing at least one resin component having a weight-average molecular weight of about 70,000 to 200,000 and one or more resin components having a weight-average molecular weight of about 150,000 to 700,000 is required when a film is thermoformed. This is preferable because irregularities can be prevented and a sufficient surface hardness can be obtained. When observing the molecular weight distribution measured by GPC on a chart, such a mixture has a shape in which the base is widened with respect to the molecular weight or a shape with a shoulder. The resin component having a weight average molecular weight of about 70,000 to 200,000 has a glass transition temperature of about 90 to 110 ° C, whereas the resin component having a weight average molecular weight of about 150,000 to 700,000 has a glass transition temperature of about 150,000 to 700,000. The thing of 40-80 ° C is preferred.

The multi-layer acrylic polymer including the rubber elastic layer is an acrylic polymer having a multi-layer structure of at least two layers, preferably three layers. Such a multi-layer acrylic polymer includes, for example, (1) an inner layer and an outer layer, wherein the inner layer is a copolymer of an alkyl acrylate having an alkyl group having 4 to 8 carbon atoms and a polyfunctional monomer such as allyl methacrylate. The outer layer is a rubber elastic body made of a polymer, and the outer layer is a two-layer acrylic polymer which is a hard polymer mainly composed of methyl methacrylate units. (2) The inner layer is composed of an inner layer, an intermediate layer and an outermost layer. The inner layer is a hard polymer having methyl methacrylate units as a main component, and the intermediate layer has an alkyl group having 4 to 4 carbon atoms.
8 is a rubber elastic body composed of a copolymer of an alkyl acrylate and a polyfunctional monomer such as allyl methacrylate, and the outermost layer is a three-layer acrylic which is a hard polymer mainly composed of methyl methacrylate units. And the like. Such a multilayer acrylic polymer can be produced, for example, by the method described in JP-B-55-27576.

The acrylic polymer having a multilayer structure containing the rubber elastic layer has a particle diameter of about 100 to 500 nm, preferably about 100 to 400 nm, and more preferably about 2 to 400 nm.
The range is 50 to 350 nm. Particle size is about 100nm
If it is less than about 500 nm, the surface hardness of the film tends to be low. If it exceeds about 500 nm, the transparency tends to be low.

The acrylic resin composition of the present invention contains the acrylic resin and a multi-layer acrylic polymer including a rubber elastic layer. The acrylic resin composition contains about 95 to 50 parts by weight of the acrylic resin and rubber. It is necessary to contain about 5 to 50 parts by weight of a multi-layer acrylic polymer including an elastic layer. Here, the total amount of the acrylic resin and the multilayer acrylic polymer including the rubber elastic layer is 100 parts by weight. If the amount of the multi-layer acrylic polymer including the rubber elastic layer is less than about 5 parts by weight, it tends to be difficult to form a film, and if it exceeds about 50 parts by weight, the surface hardness of the film tends to be low. . The preferred composition ratio is about 90 to 70 parts by weight of an acrylic resin and about 10 to 30 parts by weight of a multilayer acrylic polymer including a rubber elastic layer.

The film of the present invention may contain other polymer components and additives as long as the object of the present invention is not impaired. Other polymer components include, for example, fluorine resins such as polyvinylidene fluoride, MS (methyl methacrylate-styrene) resin, and the like. Further, as an additive, for example, an ultraviolet absorber, an antioxidant, a weathering agent such as a light stabilizer, a dye, a coloring agent such as a pigment, a flame retardant,
And inorganic fillers.

As the ultraviolet absorber, for example, a benzotriazole ultraviolet absorber, a 2-hydroxybenzophenone ultraviolet absorber, a salicylic acid phenyl ester ultraviolet absorber, a benzophenone ultraviolet absorber, and a mixture thereof are used. As the benzotriazole-based ultraviolet absorber, specifically, 2,2-methylenebis [4-
(1,1,3,3-tetramethylenebutyl) -6- (2
H-benzotriazol-2-yl) phenol], 2
-(5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (a,
a-Dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxy Phenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxy Phenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole and the like, and 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 as a 2-hydroxybenzophenone-based ultraviolet absorber. -Octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy- '- chloro benzophenone,
2,2-dihydroxy-4-methoxybenzophenone,
Examples of 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like, and examples of the phenyl salicylate-based ultraviolet absorber include para-t-butylphenyl salicylate and para-octylphenyl salicylate. Each is used alone or in combination of two or more. Above all, a high-molecular-weight benzotriazole-based ultraviolet absorber is preferable because it has a small amount of volatile components from the film and can prevent deterioration of a pattern printed on the film. Specifically, for example, 2,2-methylenebis [6- (2H benzotriazol-2-yl) -4
-(1,1,3,3-tetramethylbutyl) phenol] and the like. When such an ultraviolet absorber is used, its amount is about 0.1 part by weight or more, preferably about 0.3 to 2 parts by weight, per 100 parts by weight of the acrylic resin composition.

Examples of the antioxidant include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, and specific examples of the light stabilizer include a hindered amine-based light stabilizer.

The acrylic resin composition of the present invention can be produced, for example, by kneading an acrylic resin and a multilayer acrylic polymer containing a rubber elastic layer. When containing other polymer components or additives,
These may be contained in the acrylic resin,
It may be contained in a multilayer acrylic polymer having a rubber elastic layer, or may be added when kneading an acrylic resin and a multilayer acrylic polymer having a rubber elastic layer. Kneading conditions are not particularly limited,
It can be performed under known kneading conditions.

The acrylic resin composition of the present invention is, for example, formed into a film by extruding the film into a film, and then contacting both surfaces or one surface thereof with the roll surface to form the film. Alternatively, the film can be formed into a film by a belt cooling extrusion method in which one side is brought into contact with a belt, an inflation extrusion molding method, an extrusion casting using a chill roll, a solvent casting method, or the like. Above all, it is preferable in terms of thickness accuracy and surface smoothness of the film that the film-like material extruded into a film is formed in a state where both surfaces of the film-like material are in contact with the roll surface or the belt surface. Further, the contact of the roll surface or the belt surface may be performed by contacting one surface of the film-like material and then contacting the other surface,
It is preferred that both sides be contacted simultaneously.

The temperature of the film at the time when both surfaces of the film are first brought into contact with the roll surface or the belt surface may be at a temperature higher than the glass transition temperature of the acrylic resin composition, preferably about 20 degrees higher than the glass transition temperature. C. or higher, and the linear pressure at the time of contact is about 50 to 150 kg /
cm, preferably about 70 to 120 kg / cm.
The material of the roll surface or the belt surface is preferably made of metal because of its good cooling efficiency and easy to obtain a film having excellent smoothness, and specific examples include stainless steel and steel. When steel is used, its surface may be subjected to a treatment such as chrome plating. The temperature of the roll surface or the belt surface is not particularly limited, but is preferably kept at a constant temperature because it can be easily formed into a film. It is desirable to use three to four metal rolls and to adjust the film thickness and surface condition in multiple stages.

The thus obtained film has sufficient thickness accuracy and surface smoothness, but in order to further improve thickness accuracy and surface smoothness, both surfaces or one surface thereof are brought into contact with a roll surface or a belt surface. After heating in this state, it may be cooled.

Further, in the acrylic resin film of the present invention, even if a foreign substance having a particle diameter of 100 μm or less is contained, the appearance and printability are affected as compared with the conventional acrylic resin film. Therefore, when forming into a film, it is preferable to form after removing such foreign matter. If the foreign matter is present on the surface, specifically, when a pattern or the like is applied to one or both sides of the film by printing or the like, printing omissions or the like are likely to occur.

It is preferable to remove foreign matter by, for example, arranging a metal screen mesh, a ceramic screen mesh, or the like in the passage of the molten resin of the acrylic resin composition. In particular, it is preferable to use a rotary screen changer because clogging is small and the frequency of stopping the production process for eliminating clogging is small. As such a rotary type screen changer, a model number KSF manufactured by Gnois (Germany) is available.
−45 × 2 ”and the like. By providing such a rotary screen changer in the passage of the molten resin and extruding the resin and forming it into a film, a particle size of 10
An acrylic resin film substantially free of foreign matter of 0 μm or less can be obtained.

The thickness of the acrylic resin film of the present invention is about 0.05 to 1 mm, preferably about 0.1 to 0.6 mm.
mm, not only in the form of a film,
Sheet-like materials are also included.

The acrylic resin film of the present invention may have a pattern or the like printed on one or both sides thereof,
It may be colored. A picture or the like may be printed on a colored film. When printing a picture, depending on the colored film, an economic effect of being able to omit the base printing layer serving as the base of the printed picture can be expected.

As a method of coloring the film, a method of using a colored resin as a raw material or a method of dyeing a transparent film in a subsequent step is possible. As an example of the staining method,
10-30 g of alcohols such as benzyl alcohol
/ L and immersed in a liquid in which a disperse dye is dispersed in water containing water and dyed.

Further, an adhesive layer or an adhesive layer may be provided on one side of the acrylic resin film of the present invention. Such a pressure-sensitive adhesive layer or an adhesive layer is formed by a usual method,
For example, it can be easily provided by coating with an adhesive or an adhesive (hereinafter, simply referred to as “adhesive”).

The acrylic resin film of the present invention has sufficient thickness accuracy, excellent surface smoothness, and sufficient surface hardness. It can be used as a film, a display film, a masking film and the like.

In the simultaneous injection molding lamination using the acrylic resin film of the present invention, for example, the male and female molds of a pair of male and female molds each having a cavity space and comprising a male mold and a female mold are opened, After inserting the acrylic resin film of the present invention between the two dies, the mold is clamped with the film sandwiched between the two dies, and then the molten thermoplastic resin is injected into the cavity space. This is done by feeding and then cooling. As a result, it is possible to obtain a laminated molded article in which the film of the present invention is bonded to the surface of a molded article made of a thermoplastic resin.

The acrylic resin film of the present invention supplied between the molds may be previously formed into a desired shape by vacuum molding or the like. In this case, the thickness of the film is preferably in the range of about 0.1 to 0.5 mm from the viewpoint of shapeability. When shaping to the desired shape, a pre-formed one with a shaping mold may be supplied between the male and female molds used for injection molding. The molding may be performed using one of the molds, and the simultaneous injection molding and bonding may be performed without removing the mold from the mold.

The film may be supplied between the molds one by one, or may be supplied while unwinding a continuous film from a roll. In this case, the thickness of the film is preferably about 0.6 mm or less because it is easy to be wound into a roll, and the thickness is preferably about 0.2 mm or less from the viewpoint of winding weight (roll weight). preferable. In the case of a thickness of about 0.2 mm or more, it is advantageous to supply between the molds in the state of a single cut plate.

In the case of using a transparent acrylic resin film of the present invention having a pattern applied to one side by printing or the like, a molten thermoplastic resin is supplied to the side of the film where the pattern is applied. In the laminated molded article obtained, the film is preferably disposed on the pattern as a clear layer, and the pattern has a sense of depth, which is preferable. In this case, the thickness of the film is about 0.1 mm or more,
It is preferable because a sufficient depth feeling can be obtained.

The thermoplastic resin supplied by injection into the cavity space includes, for example, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin, polystyrene resin, polyolefin resin and the like. In terms of impact resistance and dimensional stability, ABS resin, polycarbonate resin, impact-resistant polypropylene resin and the like are preferable. Further, it is preferable that such a thermoplastic resin contains an acrylic resin, since the bonding strength between the thermoplastic resin and the film of the present invention in the obtained laminated molded article is improved. When the acrylic resin is contained in the thermoplastic resin, the content is preferably about 10% by weight or less.

The temperature, injection pressure, etc. of the thermoplastic resin in the injection are appropriately selected according to the type of the resin to be injected, the intended laminated molded product, the position of the injection gate in the mold, and the like.

When an olefin resin or the like is used as the thermoplastic resin, the surface of the film to be bonded to the thermoplastic resin in order to impart adhesiveness to the acrylic resin film of the present invention. May be subjected to a base treatment. The undercoating treatment can be performed by, for example, a method of coating a chlorinated polypropylene resin in advance.

The acrylic resin film of the present invention has excellent transparency, low transmittance of light having a wavelength of 3,000 nm or more (far infrared rays), and excellent heat insulation (heat retention), like general acrylic resin films. However, since the surface hardness is higher than that of a general acrylic resin film, it can be used as an agricultural film. Conventional acrylic resin films have to be low in surface hardness, so they tend to have low transparency due to scratches caused by dust, sand, etc. when used over a long period of time, which is a problem when used as agricultural films. Met. On the other hand, the acrylic resin film of the present invention has a sufficiently hard surface and a small decrease in transparency even when rubbed with sand or dust, so that it can be practically used as an agricultural film.

When the acrylic resin film of the present invention is used as an agricultural film, a hydrophilic polymer, a surfactant and the like may be used alone or in combination of two or more in order to impart antifogging properties. It may be contained, or may be applied to the film surface. A method for incorporating a hydrophilic polymer or a surfactant into the film and a method for applying the hydrophilic polymer or surfactant to the film surface can be performed by a known method.

Since the acrylic resin film of the present invention has excellent surface smoothness, one side thereof can be subjected to printing by an ink jet printer, gravure printing, screen printing, or the like. The acrylic resin film of the present invention on which such printing is performed is provided with an adhesive layer or the like on the surface opposite to the side on which the printing is performed, and is used as a display film for exterior / publication / advertising, that is, as a so-called marking film. Can be used. Such a display film is used by printing various characters, pictures, photographs, and the like by printing with an inkjet printer or the like using computer graphics technology.

As a display film, a soft vinyl chloride resin film, a polyurethane resin film, a polyethylene terephthalate film and the like have been conventionally used. However, a display film using the acrylic resin film of the present invention is a conventional display film. Compared with the above, it is superior in terms of appearance of the picture due to weather resistance and transparency.

When the acrylic resin film of the present invention is used as a display film, it is preferable that the total light transmittance (Tt) is 91% or more and the haze is 2% or less.
The thickness of the pressure-sensitive adhesive layer provided on one surface is preferably, for example, about 15 to 60 μm. Examples of the adhesive include an acrylic adhesive selected by subjecting a vinyl monomer composition containing an acrylic vinyl monomer and vinyl acetate to radical polymerization in a solution, and a polyurethane adhesive. Such a pressure-sensitive adhesive layer can be provided by, for example, applying a pressure-sensitive adhesive to a release material by a coating method such as a reverse roll coating method, drying by heating, and then laminating the resultant with an acrylic resin film. Here, the release material is not particularly limited, and for example, silicone-coated release paper is used.

The display film thus obtained can be cut, for example, into a desired size, figure, character, or the like as required, peeled off the release material, and laminated on a target coated substrate. Examples of the coated substrate include a plastic molded body, glass, metal, wall material, and wood. Examples of the plastic molded body include an acrylic resin, an acrylonitrile-butadiene-styrene resin, a polycarbonate resin, a vinyl chloride resin, a polystyrene resin, and a polyolefin resin.

Examples of the use of the display film include outdoor signboards (rooftop advertising towers, sleeve signboards, pole signboards, lawn signboards, canopy signs, etc.), information signs (introduction signs, display signs, information signs, station yard signs, etc.). ), Marking on commercial vehicles (fleet marking), marking on shutters and exterior walls, marking on board enclosures at factories and construction sites, marking on vending machines, marking on construction machinery, marking on railway vehicles, Examples include marking on ships, marking on tent sheets, decorative display on passenger cars, trucks, motorcycles, weak electric parts and the like as in-line members, wallpaper as interior decoration, waistboard, imitation, and the like.

The acrylic resin film of the present invention also has excellent transparency, and can be used, for example, as a masking film for protecting a base material. Conventionally, as the masking film, a film in which an adhesive layer or the like is provided on a polyethylene-based resin film has been used. However, since the polyethylene-based resin has crystallinity and is generally translucent, it is necessary to visually check the synthetic resin plate. The inspection had to be performed after the masking film was once peeled off. In addition, there is a problem that optical distortion (optical anisotropy) is likely to occur. Therefore, when used as a masking film of an optical film (for example, a polarizing film or a retardation film) used for optical applications, the Inspection of the optical film for optical distortion or the like had to be performed by peeling off the masking film.

On the other hand, since the masking film using the acrylic resin film of the present invention has excellent transparency, it is necessary to peel off the masking film by visual inspection of, for example, an acrylic resin plate or a polycarbonate resin plate. Can be done without. In addition, when used as a masking film for an optical film such as a polarizing film or a retardation film, there is no optical distortion.Therefore, inspection such as optical distortion and retardation of these optical films can be performed without removing the masking film. it can.

The acrylic resin film of the present invention may be a laminated film in which another film layer is laminated on one side. Examples of other film layers include films of ordinary acrylic resins, vinyl chloride resins, acrylonitrile-butadiene-styrene copolymers, polycarbonate resins, and olefin resins. The thickness of the other film layers is not particularly limited, but may be about 0.
It is in the range of 0.5 to 5 mm, preferably about 0.1 to 3 mm. The other film layer may be a single layer or two or more layers.

Such a laminated film may be produced by, for example, a multilayer extrusion method in which the acrylic resin film layer of the present invention and another film layer are simultaneously extruded and laminated, or the acrylic resin film layer of the present invention which is separately produced. You may manufacture by bonding a resin film and another film. Further, another film layer may be extruded into a film shape, and the acrylic resin film of the present invention may be bonded to the heated film immediately after the extrusion, and immediately after bonding, the acrylic resin film may be bonded to the film. By bringing the acrylic resin film layer of the invention and another film layer into contact with the roll surface or the belt surface, a laminated film can be obtained.

When such a laminated film uses a film layer other than the acrylic resin film layer as the other film layer, it is used so that the outside thereof becomes the acrylic resin film of the present invention. It is preferable because the surface is clear and a transparent feeling can be obtained. Further, when the laminated film is an acrylic resin film layer and the acrylic resin film layer of the present invention, the outside thereof is a normal acrylic resin film layer (for example, an acrylic resin film layer containing no rubber elastic body). It can also be used so that the inside becomes the acrylic resin film layer of the present invention. In this case, a laminated film having excellent surface hardness, chemical resistance, weather resistance, and the like can be obtained. Further, it is difficult to wind a conventional acrylic resin film containing no rubber elastic body into a roll by itself, but such a laminated film can be wound into a roll, which is also advantageous in this respect. Here, the rubber elastic body includes a multi-layer acrylic polymer including the rubber elastic body layer described above.

In such a laminated film, a non-colored acrylic resin film and a colored acrylic resin film, or a non-colored acrylic resin film and a colored olefin resin (particularly, impact-resistant polypropylene resin)
In the laminated film with the film, the effect of increasing the sense of quality with the colored film layer appearing as a deep color through an uncolored acrylic resin film is recognized. In addition, by including 1 to 10% by weight of metal powder (particularly, flat aluminum powder, etc.), mica, etc. in a colored or uncolored film layer, it is possible to obtain an effect commonly called metallic tone or pearl tone. Become.

[0051] Such a laminated film is made of an acrylic resin film because of its excellent weather resistance and surface hardness. In particular, it is used for automobile outer plates such as bumpers, garnishes and side moldings, or home electric appliances such as refrigerators, air conditioners, and washing machines. It is useful as a substitute for painting. By using this coating substitute film, it is also possible to prevent environmental pollution by an organic solvent contained in a coating material used for general coating. In such a laminated film, usually, a non-colored acrylic resin film is used so as to be on the outside, and another resin by injection molding, a metal by bonding, or the like can be used as a base.

When the acrylic resin film and the colored olefin resin film are bonded, a chlorinated polypropylene resin, an ethylene-methyl methacrylate copolymer resin, a maleic anhydride-modified polypropylene resin, or the like is included in the olefin resin film. It is effective to carry out the coating or to coat these resins on the surface. Furthermore, it is also possible to laminate an acrylic resin film and a colored olefin resin by a lamination method using a urethane-based adhesive or the like.

In the case of a laminated film, the pattern may be printed on the surface of an acrylic film or on the surface of another film. For example, when the other film layer is a vinyl chloride-based resin film, a pattern or the like can be easily printed on one surface thereof, and the acrylic resin film of the present invention is laminated thereon to obtain a transparent feeling. And a laminated film having excellent design properties can be obtained. Lamination can be performed, for example, by heating and pressing the acrylic resin film and the vinyl chloride resin film of the present invention, and the heating temperature is about 80 to 200 ° C. The laminated film can be used as, for example, agricultural materials such as greenhouses, architectural materials such as arcades and soundproofing boards, and exterior materials such as sunroofs. The laminated film is
Like a single-layer acrylic resin film, it can be used as a film for simultaneous lamination with injection molding, an agricultural film, and a display film.

When used in the simultaneous injection molding laminating method, it can be carried out in the same manner as in the above-mentioned acrylic resin film of the present invention. When used as an agricultural film, preferred examples of the other film include a vinyl chloride resin film, a polyolefin resin film, a polyvinyl alcohol resin film, a polyethylene terephthalate film, and a polycarbonate film.

Further, when used as a display film, the acrylic resin film of the present invention is used so as to be the outermost layer, and an adhesive layer is provided on the side of the other film layer. The other film layer may be colored, or a pattern may be provided between the acrylic resin film of the present invention and the other film layer by printing or the like. By the acrylic resin film of the present invention is the outermost layer,
These give a sense of depth and improve the design.

It is preferable that the acrylic resin film in the display film has a total light transmittance (Tt) of 91% or more and a haze of 2% or less. Further, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer provided on one surface, the thickness thereof,
It has the same pressure-sensitive adhesive and thickness as when a single-layer acrylic resin film is used as a display film, and can be provided as a pressure-sensitive adhesive layer in the same manner as described above. The method of use and the use are the same as those in the case where the acrylic resin film of the present invention is used as a display film.

[0057]

The acrylic resin film and its multilayer film of the present invention are suitable for various uses such as a film for simultaneous lamination of injection molding, a film for agricultural use, a display film, a masking film and a substitute film for painting. In particular, a film obtained by coloring or printing a pattern on this film is superior to a conventional acrylic film in terms of the depth and luxurious feeling when laminated and the printability of the pattern.

[0058]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The evaluation method is as follows. (1) Thickness Accuracy Using a dial gauge with an accuracy of 1/1000 mm, the thickness of the film was continuously measured for each 1 m in the width direction and the take-off direction, and the average thickness (d ₀ ), the maximum thickness (d _max ),
Calculated minimum thickness of (d _min), respectively, the average thickness (d ₀₎ and the maximum thickness (d _{m ax)} difference or average thickness of the (d ₀₎ and towards the larger among the difference between the minimum thickness (d _min) Assuming that the thickness is Δd, the thickness was calculated by the following formula (1): thickness accuracy (%) = (Δd / d ₀ ) × 100 (1) (2) Irregularity generation test during molding The surface state of the obtained laminated molded body was visually observed, and judged according to the following criteria. ：: Almost no irregularities on the surface △: Slight irregularities on the surface ×: Fine irregularities on the surface (3) Gauze abrasion Friction tester for measuring color fastness [Toyo Seiki Co., Ltd. Manufacturing
D-type] measuring jig with gauze,
An abrasion test of 00 reciprocations was performed, and evaluated visually by the following criteria. ：: No abrasion is observed. Δ: Abrasion is slightly observed. X: Abrasion is clearly observed. (4) Surface hardness Pencil hardness was measured according to JIS K5400. (5) Optical performance According to JIS K 6718, total light transmittance (Tt)
And haze were measured. (6) Glass transition temperature Using a differential scanning calorimeter (DSC), the endothermic onset temperature observed when the temperature was raised at a rate of 10 ° C./min under a stream of N 2 was determined by the tangential method. (7) Weight average molecular weight Measured by gel permeation chromatography (GPC). (8) Number of Missing Prints A pattern was gravure-printed on one side of the film, the number of missing prints was visually inspected on the front surface of the film having a width of 1 m and a length of 10 m, and the number was converted to 1 m ² .

The meanings of the symbols in the examples are as follows. (1) Acrylic resin I: manufactured by a bulk polymerization method, comprising 99% by weight of methyl methacrylate units and 1% by weight of methyl acrylate units, and having a glass transition temperature of 1
A resin having a weight average molecular weight of 140,000 at 140 ° C. (2) Acrylic resin II: manufactured by a bulk polymerization method, comprising 90% by weight of methyl methacrylate unit and 10% by weight of methyl acrylate unit, having a glass transition temperature of 95 ° C. and a weight average molecular weight of 120,000. Some resin. (3) Acrylic resin III: manufactured by a suspension polymerization method, comprising 80% by weight of methyl methacrylate units and 20% by weight of butyl acrylate units, and having a glass transition temperature of 6
A resin having a weight average molecular weight of 300,000 at 2 ° C. (4) Acrylic resin IV: manufactured by a suspension polymerization method, comprising 80% by weight of methyl methacrylate units and 20% by weight of butyl acrylate units, and having a glass transition temperature of 6
A resin having a weight average molecular weight of 500,000 at 2 ° C. (5) Acrylic resin V: produced by a suspension polymerization method, comprising 70% by weight of methyl methacrylate units and 30% by weight of methyl acrylate units, and having a glass transition temperature of 4
A resin having a weight average molecular weight of 300,000 at 7 ° C.

(6) Acrylic polymer A: Japanese Patent Publication No. 555-2
With reference to Example 3 of Japanese Patent No. 7576, it was produced as follows, wherein the innermost layer was a methyl methacrylate crosslinked polymer, the intermediate layer was a soft rubber elastic body mainly composed of butyl acrylate, A spherical three-layer acrylic polymer whose outer layer is made of a methyl methacrylate polymer. The average particle size of the polymer particles is about 300 nm. Distilled water, potassium carbonate, dioctyl sulfosuccinate and potassium persulfate were charged into a glass container (capacity: 5 liters) equipped with a cooler, and stirred under a nitrogen atmosphere. Then, 38 parts of methyl methacrylate and 0.08 part of allyl methacrylate were added. I charged. The mixture was reacted at 70 ° C. for 30 minutes to obtain an innermost layer polymer. Subsequently, 38 parts of butyl acrylate and 9 parts of styrene
Part of a monomer mixture of 1 part by weight of allyl methacrylate, 9 parts of a mixture of potassium persulfate and dioctyl sulfosuccinate.
The mixture was continuously added over 0 minutes and held for 90 minutes to polymerize the crosslinked elastic layer of the intermediate layer. Finally, a mixture of 14 parts of methyl methacrylate, 0.6 part of ethyl acrylate, and potassium persulfate is continuously added over 60 minutes, and further maintained for 60 minutes to polymerize the outermost layer. A polymer was obtained. The final average particle diameter of the polymer particles measured by an electron microscope was 300 nm. The polymer latex was coagulated according to a conventional method, and then dehydrated and dried to obtain a dry powder. (7) Acrylic polymer B: produced without forming the innermost layer according to the production method of acrylic polymer A,
The inner layer is made of a soft rubber elastic body containing butyl acrylate as a main component, and the outer layer is made of a spherical rubber made of a methyl methacrylate polymer.
Layered acrylic polymer. The average particle size of the polymer particles is about 300 nm.

(8) UV absorber LA31: "Adeka stub LA-31" (high molecular weight benzotriazole type) manufactured by Asahi Denka Kogyo KK (9) UV absorber 250: "Sumisorb" manufactured by Sumitomo Chemical Co., Ltd. 250 "(10) Aluminum powder: manufactured by Toyo Aluminum Co., Ltd., aluminum paste (11) Titanium oxide powder: manufactured by Kanto Chemical Co., Ltd., titanium oxide powder (12) Disperse dye: manufactured by Sumitomo Chemical Co., Ltd. Karon Red E-FBL "

REFERENCE EXAMPLE 1 Each raw material was mixed at a composition ratio shown in Table 1 by a tumbler type mixer, and the resin temperature was set to 255 ° C. using a co-rotating twin screw extruder.
While kneading while maintaining the acrylic resin composition a
~ I pellets were obtained.

Examples 1 to 8 A pellet of each acrylic resin composition shown in Table 2 was subjected to a T-type film die [a lip clearance of 0.5 mm, using a single-screw extruder (barrel type 65 mmφ, manufactured by Toshiba Machine Co., Ltd.)]
Extruded through a width of 600 mm and a set temperature of 250 ° C.] to obtain a film-like material. Immediately, both surfaces were simultaneously and completely brought into contact with the surface of a cooling polishing roll to form an acrylic resin film [thickness of 0.13 mm]. Was. Table 2 shows the evaluation results of this film.

A woodgrain pattern is printed on one side of this film by printing and placed in a cavity of an injection molding mold (mold temperature 50 ° C.) comprising a pair of male and female molds for injection molding. Then, after heating with a far-infrared heater, vacuum forming was performed to shape. Then, the heated and melted ABS resin (resin temperature 230 ° C.) was injected at an injection pressure of 1150 kg / cm ^2.
And then cooled to obtain a laminated molded article in which an acrylic resin film was bonded to the surface of the ABS resin molded article. Table 2 shows the results of the evaluation of the laminate.

Examples 9 to 10 In the same manner as in Examples 1 and 4, except that only one surface of the film was brought into contact with the surface of the cooling polishing roll instead of contacting both surfaces of the film with the surface of the cooling polishing roll. Thus, an acrylic resin film [thickness 0.13 mm] was obtained, and then a laminated molded product was obtained. Table 2 shows the evaluation results of the acrylic resin film and the laminate.

Example 11 The acrylic resin film obtained in Example 10 was heated while cooling both sides while being in contact with a continuous stainless steel belt, to obtain an acrylic resin film. Table 2 shows the evaluation results of the acrylic resin film. The same operation as in Example 1 was performed except that the acrylic resin film obtained above was used instead of the acrylic resin film obtained in Example 1,
A laminated molded article was obtained. Table 2 shows the results of the evaluation of the laminate.

Example 12 Using a single-screw extruder (barrel diameter: 65 mmφ, manufactured by Toshiba Machine Co., Ltd.), a T-type film die [lip clearance: 4 m]
m, width 600 mm, set temperature 280 ° C.], the acrylic resin film obtained in Example 1 was extrusion-laminated simultaneously on the surface of the polycarbonate resin sheet being extruded, and both sides were completely contacted with a polishing roll, A laminated film (thickness: 3 mm) was obtained. Table 2 shows the evaluation results of the laminated film.

Example 13 A laminated film (thickness: 3 mm) was obtained in the same manner as in Example 12, except that the acrylic resin film obtained in Example 4 was used instead of the acrylic resin film obtained in Example 1. Was. Table 2 shows the evaluation results of the laminated film.

Example 14 The acrylic resin film obtained in Example 1 was laminated on the printed pattern side of a 0.1 mm-thick soft vinyl chloride film having a carbon pattern printed on the surface to obtain a laminated film. After shaping this laminated film by thermoforming, it is inserted into a mold for injection molding (mold temperature 50 ° C.), and then polycarbonate resin is injected [injection pressure 1250 kg / c.
m ² , resin temperature: 280 ° C.] and simultaneous lamination with injection molding was performed to obtain a laminated molded body in which a laminated film was laminated on a polycarbonate resin layer (thickness: 3 mm).

Example 15 An inorganic red pigment was kneaded with the composition d to obtain a pellet of the composition d ', which was supplied to a single screw extruder [barrel system 65 mmφ, manufactured by Toshiba Machine Co., Ltd.]. In addition, a pellet of the composition i is fed to a single screw extruder [a barrel diameter of 45 mmφ manufactured by Hitachi Zosen Corporation].
Supplied. A two-layer multi-manifold type film die connected to a twin-screw extruder [lip clearance 0.5
mm, a width of 600 mm, and a set temperature of 250 ° C.) to extrude the composition d ′ and the composition i from the respective single screw extruders,
A cooling polishing roll (made of stainless steel) is formed by completely contacting both sides with a thickness of 0.3 mm (a red layer of 0.2 m).
m, transparent layer 0.1 mm). Table 2 shows the evaluation results of the laminated film.

The laminated film was placed in an injection mold (at a temperature of 50 ° C.) so that the transparent layer was in contact with the mold surface, heated by a far-infrared heater, vacuum-formed, and then Inject acrylonitrile-butadiene-styrene resin (ABS resin) onto the surface [injection pressure 1150 kg /
cm ² and a resin temperature of 230 ° C.] to perform simultaneous lamination with injection molding to obtain a laminated molded body in which a laminated film is laminated on an ABS resin layer (thickness: 3 mm). Table 2 shows the results of the evaluation of the laminate.

Example 16 A composition obtained by mixing an aluminum paste into a composition b (100 parts by weight) so as to be 2 parts by weight in terms of aluminum was subjected to a twin-screw extruder (PCM, manufactured by Ikegai Iron Works Co., Ltd.) -45) to obtain pellets colored in silver metallic color. The colored pellets are formed by a single screw extruder (manufactured by Toshiba Machine Co., Ltd.
And a pellet of the composition i is supplied to a single screw extruder [manufactured by Hitachi Zosen Corporation, barrel diameter 45 mm].
φ], and through a feedblock type multilayer die [manufactured by Hitachi Zosen Corporation, lip surface length 600 mm] connected to the two extruders, the surface layer is a transparent acrylic resin film, and the lower layer is a silver metallic acrylic. A laminated film composed of a base resin film was formed by completely contacting both sides with a cooling polishing roll (made of stainless steel). The film thickness was 0.5 mm. This film was a silver metallic colored laminated film having a deep surface gloss.

A chlorinated polypropylene resin (“No. 822” manufactured by Nippon Paper Industries Co., Ltd.) is provided on the lower layer side of the laminated film.
After being coated in a mold for injection molding (temperature: 50 ° C.) so that the surface layer is in contact with the mold surface, and heated by a far-infrared heater, vacuum molding (area development rate: 1.3) Times). Next, on the lower layer side, a polypropylene resin [Sumitomo Chemical Co., Ltd., “Sumitomo Noblen”
BYA81] (injection pressure 1150 kg / cm ² ,
At a resin temperature of 250 ° C.], simultaneous lamination with injection molding was carried out to obtain a laminated molded body in which a silver metallic laminated film was integrally laminated on a polypropylene resin layer (thickness: 3 mm). The surface of this laminated molded article had a deep surface gloss, and the polypropylene resin layer and the laminated film were firmly bonded.

Example 17 White colored pellets were obtained in the same manner as in Example 16 except that 5 parts by weight of titanium oxide in terms of titanium oxide was used instead of the aluminum paste. Using this colored pellet, a laminated film was formed in the same manner as in Example 16. The film thickness was 0.5 mm. This film was a white laminated film having a deep surface gloss.

Example 18 10 g of a red disperse dye was dispersed in distilled water containing 18 g of benzyl alcohol, and the acrylic resin film obtained in Example 1 (thickness: 0.1 liter) was dispersed in a dyeing solution (1 liter) heated to 80 ° C. 13 mm) and stained. The color tone of the dyed film was examined by the color difference display method of JIS Z-8730, and the result was L * = 86.0, a * = 22.
8, b * =-5.4, which was uniform. When gravure printing a woodgrain pattern on one side of this film, the base underprinting layer on the entire surface was omitted, and only the pattern was printed.

Comparative Example 1 A commercially available soft acrylic film [Mitsubishi Rayon Co., Ltd.
“Acryprene HBS-001”, thickness 100 μm]
Then, the same woodgrain pattern as in Examples 1 to 8 was printed, and the printed film was placed in an injection mold (at a temperature of 5).
After warming with a far-infrared heater at 0 ° C), vacuum forming was performed, and then ABS resin was injected to the back surface to a thickness of 3 mm (injection pressure 1150 kg / cm ² , resin temperature 230 ° C).
Then, a laminated molded body on which the print film was bonded was obtained. Table 2 shows the evaluation results of the obtained film and the laminate. The acrylic film (HBS-001) contained a large number of single-layer rubber elastic bodies having a particle diameter of less than 100 nm, but it was observed by a transmission electron microscope that it did not contain an acrylic polymer having a multilayer structure. ,confirmed.

[0078]

[Table 1]

[0079]

[Table 2]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Koyama 2-1-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Co., Ltd. F-term (reference) 4F100 AB01B AC06B AK01B AK03B AK15B AK25A AK25B AK25J AK74B AL01A AL05A AL09A AN00A BA01 BA02 DE01A DE01B EH36 EJ24 EJ43 GB01 GB33 GB48 GB90 HB01A HB31A JA05A JA07A JK12 JK15 JL10A JL10B YY00A 4F206 AA03 AA13 AA15 AA21 AD05 AD08 AD29 AD34 AG03 AH01 BG04 BG04 BG04 BG04 FD070 GA01

Claims (16)

[Claims] An acrylic resin 95 having a glass transition temperature of 60 to 110 ° C. and a weight average molecular weight of 70,000 to 600,000.
An acrylic resin film comprising an acrylic resin composition containing 50 to 50 parts by weight of a multilayer acrylic polymer having a rubber elastic layer and 50 to 50 parts by weight. 2. The acrylic resin film according to claim 1, wherein the acrylic resin is a polyalkyl methacrylate or a copolymer of an alkyl methacrylate and an alkyl acrylate. 3. A multi-layer acrylic polymer comprising a rubber elastic layer, comprising: (1) an inner layer and an outer layer, wherein the inner layer comprises an alkyl acrylate having an alkyl group of 4 to 8 carbon atoms and a polyfunctional monomer. The outer layer is a hard polymer mainly composed of methyl methacrylate units.
Layered acrylic polymer or (2) an innermost layer, an intermediate layer and an outermost layer, wherein the innermost layer is a hard polymer mainly composed of methyl methacrylate units, and the intermediate layer has an alkyl group having a carbon number of alkyl group. Rubber elastic body composed of a copolymer of an alkyl acrylate of 4 to 8 and a polyfunctional monomer, and the outermost layer is a hard polymer mainly composed of methyl methacrylate units.
The acrylic resin film according to claim 1, which is a layered acrylic polymer. 4. A multilayer acrylic polymer having a particle size of 10
The acrylic resin film according to claim 1, which has a thickness of 0 to 500 nm. 5. The acrylic resin film according to claim 1, wherein the acrylic resin composition is formed by melt-extrusion molding the acrylic resin composition so that both surfaces of the film are in contact with a roll surface or a belt surface. 6. The acrylic resin film according to claim 1, which is colored by a dyeing method. 7. A laminated film obtained by laminating another resin film layer on one side of the acrylic resin film according to claim 1. 8. The laminated film according to claim 7, wherein the other resin film is a vinyl chloride resin film. 9. The laminated film according to claim 7, wherein the other resin film is a colored acrylic resin film or a colored olefin resin film. 10. The laminated film according to claim 9, wherein the colored acrylic resin film or the colored olefin resin is obtained by adding metal powder or mica. 11. A masking film comprising the acrylic resin film according to claim 1. 12. A film for simultaneous lamination with injection molding, comprising the film according to claim 1 or 7. 13. An agricultural film comprising the film according to claim 1 or 7. 14. A display film comprising the film according to claim 1 or 7. 15. A coating substitute film comprising the film according to claim 9. 16. The film according to claim 1 or 7 is inserted into a male and female mold, and the film is simultaneously bonded to the surface of a molded product obtained by injection molding a thermoplastic resin in the mold. Laminated molded article.