JP2003238704A - Acrylic resin film, method for manufacture the same and laminated sheet of the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare an acrylic resin film excellent in peeling property between a base material sheet and a heating roll which is used when heat laminating of the film while keeping the original merits of the acrylic resin such as good molding property, beautiful appearance, high transparency and excellent weathering property, and to provided a laminated sheet high in industrial productivity. <P>SOLUTION: This acrylic resin film has a peeling strength of not higher than 30 kgf when measured by preparing a film cut out in ϕ 10 mm, and sandwiching it between metal plates each having a surface roughness of #250 and heating the sandwiched material at 170°C for 8 minutes under a load of 7 kg, then peeling the one metal plate in the direction perpendicular to the surface of the metal plates, and a surface gloss of 80-120%, and a method for manufacturing the film and the laminated sheet obtained from the acrylic resin films are provided. <P>COPYRIGHT: (C)2003,JPO

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 suitable for a laminated sheet, which is laminated with a thermoplastic resin film or sheet, a method for producing the same, and an acrylic resin film laminated sheet obtained by laminating the film. .

[0002]

2. Description of the Related Art Acrylic resin is excellent in transparency, has a beautiful appearance and weather resistance, and is easy to mold. Therefore, it is suitable for electrical parts, vehicle parts, optical parts, ornaments, signs, etc. Widely used. However, as the applications of acrylic resins have expanded, further improvement of performance according to the applications has been studied. Of these, acrylic resin films have recently been used in various industrial fields for the purpose of imparting surface functions to various resin molded products. These acrylic resin films are used by being laminated on base resin molded products such as polycarbonate resin, polyethylene resin, polypropylene resin, vinyl chloride resin, vinylidene fluoride resin, methacrylic resin, ABS resin, AES resin, AS resin, It is applied to imparting weather resistance and scratch resistance to these substrates. As a method for laminating an acrylic resin film on a base material sheet or the like, there are a thermal laminating method in which a film is heated and laminated on a base material, a dry laminating method in which an adhesive is applied to the film and the film is attached to a base material sheet, A thermal laminate in which an acrylic resin film is preheated with a heating roll, laminated on a base material sheet, and then laminated by sandwiching a laminate between a plurality of rolls to bond the acrylic resin film is most industrially widely used. But,
In this thermal laminating method, the acrylic resin film is difficult to peel off from the preheating roll due to long-term continuous operation, and there is a problem of winding around the heating roll. Further, in the thermal laminating method, in the step of sandwiching the laminate composed of the base material sheet and the acrylic resin film with a plurality of rolls, the acrylic resin side is unlikely to be peeled off from the rolls due to long-term continuous operation, and may be wound around the rolls during sandwiching. There was a problem.
In order to prevent wrapping around these rolls, there are methods such as lowering the temperature of the preheating roll and lowering the pressure of the sandwich roll. However, there is a problem in that the embossing followability deteriorates when an uneven surface is formed by using an embossing roll, and a laminated body cannot be manufactured stably.

On the other hand, the dry laminating method has problems that it uses an organic solvent or an adhesive and that it has problems with the environment and that the manufacturing cost is higher than that of the thermal laminating method.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a base material sheet while maintaining the characteristics such as good moldability, beautiful appearance, high transparency, and excellent weather resistance that the acrylic resin originally has. An object of the present invention is to provide an acrylic resin film having excellent releasability from a heating roll at the time of thermal lamination, and to provide a laminated sheet industrially rich in production.

[0005]

The gist of the present invention is φ10.
The film cut into mm is sandwiched between metal plates having a surface roughness of # 250, and a load of 7 kg is applied at 170 ° C. for 8 minutes for pressing, and then the peel strength when the metal plate is vertically peeled off is 30 kgf or less. And has a surface gloss of 80-
120% acrylic resin film, its manufacturing method and its laminated sheet.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below.

The acrylic resin film of the present invention has a diameter of φ10.
A film having a thickness of mm is sandwiched between metal plates having a surface roughness of # 250, a load of 7 kg is applied thereto, and after pressing at 170 ° C. for 8 minutes, the metal plate must have a strength of not more than 30 kgf when peeled off. 30kg strength when peeling off a metal plate
If it exceeds f, when the acrylic resin film is thermally laminated with the substrate sheet, the peeling property from the sandwiching roll becomes poor, and winding around the roll occurs, and a laminated sheet cannot be manufactured stably.

On the other hand, the surface gloss of the acrylic resin film of the present invention must be 80 to 120%. When the surface gloss of the acrylic resin film is less than 80%, the transparency originally possessed by the acrylic resin film is impaired, and
If it exceeds 0%, the releasability from the heating roll deteriorates, so that winding around the preheating roll occurs and a laminated sheet cannot be manufactured stably. The more preferable surface gloss of the acrylic resin film is 90 to 120%.
This surface gloss is a gloss value at a measurement angle of 60 ° measured by ASTM D523.

The acrylic resin (composition) constituting the acrylic resin film of the present invention is not particularly limited, but a film composition made of a known acrylic resin, for example, Japanese Patent Publication No. 62-19309. 63-
It is preferable to use the acrylic resin compositions disclosed in JP-A-20459, JP-A-63-77963, JP-A-8-323934 and the like.

Preferred examples of the acrylic resin (I) used in the production of the acrylic resin film of the present invention include alkyl acrylates, alkyl methacrylates and graft cross-linking agents which are known in the art as constituents of the polymer. An acrylic resin film which is a multi-layered polymer and which is used as a film raw material has excellent weather resistance, transparency and stress whitening resistance.

Specific examples of the more preferable multilayer structure polymer include at least an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and / or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms and a graft crossing agent. The innermost layer polymer (A) layer which is a constituent component of the above, a crosslinked elastic polymer (B) which is a polymer having an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and a graft crossing agent as a constituent component, and a carbon number of 1
To the outermost layer polymer (C) which is at least an alkyl methacrylate having an alkyl group as a constituent of the polymer as a basic structure, and further has a crosslinked elastic polymer (B) layer and an outermost layer polymer (C). 1 to 8 carbon atoms between layers
Alkyl acrylate having an alkyl group of 1 carbon number
An alkyl methacrylate having an alkyl group of 4 to 4 and a graft crossing agent as at least constituents,
Further, it is a multilayer structure polymer having at least one intermediate layer (D) in which the amount of alkyl acrylate component monotonically decreases from the crosslinked elastic polymer (B) layer toward the outermost polymer (C) layer.

The innermost layer polymer (A) which constitutes a preferable multilayer structure polymer is an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or an alkyl methacrylate (A1) having an alkyl group having 1 to 4 carbon atoms, Other monomer having a copolymerizable double bond (A
2) and a polyfunctional monomer (A3) used as necessary
And a graft crossing agent (A4) as a constituent component, and constitutes a basic structure of at least the innermost layer of the multilayer structure.

Component (A) constituting the innermost layer polymer (A)
In 1), the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms may be linear or branched.
Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate and the like. These may be used alone or in admixture of two or more. Among these, those having a low glass transition temperature (hereinafter referred to as “Tg”) are more preferable. The alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms in the component (A1) may be linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like. These may be used alone or in admixture of two or more.

Alkyl (meth) acrylate (A1)
Is preferably used within the range of 80 to 100 parts by mass with respect to 100 parts by mass of the total amount of the components (A1) to (A3). It is most preferable to use the same type of alkyl (meth) acrylate used in the innermost layer polymer (A) in all subsequent multi-layers. However, two or more kinds of alkyl (meth) acrylates may be mixed or different kinds of acrylates may be used in each of all the multi-stage layers. In addition, "(meth) acrylate" shall mean an acrylate and / or a methacrylate.

The other monomer (A2) having a copolymerizable double bond constituting the innermost layer polymer (A) may be used if necessary. Specific examples thereof include higher alkyl acrylate having an alkyl group having 9 or more carbon atoms, lower alkoxy acrylate, acrylate monomer such as cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacryloyl. Examples include nitrile and the like. The monomer (A2) is preferably used within a range of 0 to 20 parts by mass based on 100 parts by mass of the components (A1) to (A3) in total.

The polyfunctional monomer (A3) constituting the innermost layer polymer (A) may be used if necessary. Specific examples thereof include ethylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,4-
It is preferable to use alkylene glycol dimethacrylates such as butylene glycol dimethacrylate and propylene glycol dimethacrylate. Also, polyvinylbenzene such as divinylbenzene and trivinylbenzene can be used. In addition, a polyfunctional monomer (A3)
Gives a multilayer polymer which is fairly stable as long as the graft crossing agent is present. For example, when hot strength or the like is strictly required, it may be optionally used according to the purpose of addition. Polyfunctional monomer (A
It is preferable to use 3) in the range of 0 to 10 parts by mass with respect to 100 parts by mass of the components (A1) to (A3) in total.

Examples of the graft crossing agent (A4) constituting the innermost layer polymer (A) include allyl, methallyl or crotyl ester of a copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Particularly, acrylic acid, methacrylic acid, maleic acid or fumaric acid acrylic ester is preferable. Of these, allyl methacrylate is particularly effective. In addition, triallyl cyanurate and triallyl isocyanurate are also effective. In the graft crossing agent (A4), the conjugated unsaturated bond of the ester mainly reacts much faster than the allyl group, methallyl group or crotyl group, and is chemically bonded. During this time, a substantial part of the allyl group, methallyl group or crotyl group works effectively during the polymerization of the next layer polymer to provide a graft bond between the adjacent two layers.

The amount of the graft crossing agent (A4) used is important, and is preferably 0.1 to 5 parts by mass, and 0.5 to 2 parts by mass based on 100 parts by mass of the total amount of the components (A1) to (A3). Is more preferable. The lower limit of these ranges is significant in terms of the effective amount of graft bond. In addition, the upper limit is to appropriately suppress the reaction amount with the crosslinked elastic polymer (B) formed by polymerization in the second stage and prevent the elasticity of the two-layer crosslinked rubber elastic body having the two-layer elastic body structure from being lowered. it makes sense.

The content of the innermost layer polymer (A) in the preferred multilayer structure polymer is preferably 5 to 35% by mass, and 5 to 15% by mass.
Mass% is more preferable. Further, the content is preferably smaller than the content of the crosslinked elastic polymer (B).

The crosslinked elastic polymer (B) which constitutes a preferable multilayer structure polymer is a main component which imparts rubber elasticity to the multilayer structure polymer, and is an alkyl acrylate (B1) having an alkyl group having 1 to 8 carbon atoms. And another monomer (B2) having a copolymerizable double bond, which is used if necessary,
It is a crosslinked elastic polymer comprising a polyfunctional monomer (B3) used as necessary and a graft crossing agent (B4) as constituent components.

Preferred specific examples of the components (B1) to (B4) are the components (A1) to (A) of the innermost layer polymer (A), respectively.
It is the same as that mentioned in 4). The amount of component (B1) used is preferably 80 to 100 parts by mass. The amount of component (B2) used is preferably 0 to 20 parts by mass. The amount of component (B3) used is preferably 0 to 10 parts by mass. The amount of component (B4) used is preferably 0.1 to 5 parts by mass. These usage ranges are
The total of components (B1) to (B3) is 100 parts by mass.

The Tg of the crosslinked elastic polymer (B) alone is 0 ° C.
The following is preferable, and −30 ° C. or less is more preferable. This T
When g is 0 ° C. or less, excellent elasticity tends to be exhibited. The content of the crosslinked elastic polymer (B) in the multilayer structure polymer (E) is preferably 10 to 45% by mass, and is preferably larger than the content of the innermost layer polymer (A).

The outermost layer polymer (C) which constitutes a preferable multilayer structure polymer is a component involved in the moldability and mechanical properties of the multilayer structure polymer, and is an alkyl having an alkyl group having 1 to 4 carbon atoms. Methacrylate (C1) and another monomer (C) having a double bond capable of copolymerization, which is optionally used.
2) is a polymer having and as constituent components, and constitutes at least the outermost layer of the basic structure of the multilayer structure.

Preferred specific examples of the components (C1) and (C2) are the same as those listed as the components (A1) and (A2) of the innermost layer polymer (A), respectively. Ingredient (C1)
The amount of use of 51 to 100 parts by mass is preferable. Ingredient (C
The amount of 2) used is preferably 0 to 49 parts by mass. The range of these amounts used is 100 in total of the components (C1) and (C2).
Based on parts by mass.

The outermost layer polymer (C) alone has a Tg of 60 ° C.
The above is preferable, and 80 ° C or more is more preferable. The content of the outermost layer polymer (C) in the multilayer structure polymer is preferably 10 to 80% by mass, more preferably 40 to 60% by mass.

A preferred multilayer structure polymer has the innermost layer polymer (A), the crosslinked elastic polymer (B) and the outermost layer polymer (C) described above as basic structures. Further, an intermediate layer (D) is provided between the crosslinked elastic polymer (B) layer and the outermost layer polymer (C) layer.

The intermediate layer (D) is optionally used with an alkyl acrylate (D1) having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate (D2) having an alkyl group having 1 to 4 carbon atoms. Another monomer (D3) having a copolymerizable double bond, a polyfunctional monomer (D4) used as necessary, and a graft crossing agent (D5) are used as constituent components of the polymer, In addition, the amount of alkyl acrylate component monotonically decreases from the crosslinked elastic polymer (B) layer toward the outermost polymer (C) layer.

The term "monotonically decreasing" as used herein means that the intermediate layer (D) has a composition at a certain point intermediate between the crosslinked elastic polymer (B) and the outermost layer polymer (C), from the crosslinked elastic polymer (B). It means that the composition gradually (continuously) approaches the outermost layer polymer (C), and that the composition gradually approaches, and in particular, a composition having one intermediate composition is advantageous in terms of productivity. Good.

Preferred specific examples of the components (D1) to (D5) are components (A1) to (A) of the innermost layer polymer (A), respectively.
It is the same as that mentioned in 4). In particular, the graft crossing agent (D5) used in the intermediate layer (D) is a component necessary for closely bonding the polymer layers and obtaining excellent properties.

The amount of component (D1) used is preferably 10 to 90 parts by mass. The amount of component (D2) used is preferably 10 to 90 parts by mass. The amount of component (D3) used is preferably 0 to 20 parts by mass. The amount of component (D4) used is preferably 0 to 10 parts by mass. The amount of component (D5) used is preferably 0.1 to 5 parts by mass. The range of these amounts used is components (D1) to (D
Based on the total of 100 parts by weight of 4).

Intermediate layer (D) in the preferred multilayer structure polymer
The content of is preferably 5 to 35% by mass. When the content is 5% by mass to 35% by mass, an acrylic resin film having excellent flexibility and processability can be obtained.

The preferred average particle size of the multilayer structure polymer used in the production of the acrylic resin film of the present invention is 0.08-0. The range of 2 μm is preferable.

The above-mentioned multi-layer structure polymer is an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and / or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms and a graft which gives the innermost layer polymer (A) layer. An emulsion prepared by mixing a monomer mixture containing at least a crossing agent with water and a surfactant is supplied to a reactor for polymerization, and then a crosslinked elastic polymer (B) layer, an intermediate layer (D) and an outermost layer. A monomer or a mixture of monomers which gives the polymer (C) can be supplied to the reactor in sequence and polymerized, thereby reducing huge polymer particles existing in the acrylic resin latex and distributed in the range of 1 to 200 μm. It is preferable in that

The weight ratio of the monomer mixture of the acrylic resin latex and water is preferably 10 parts to 500 parts of water relative to 100 parts of the monomer mixture, and more preferably water to 100 parts of the monomer mixture. It is in the range of 100 to 300 parts.

As the surfactant used when preparing the emulsion, anionic, cationic and nonionic surfactants can be used, but anionic surfactants are particularly preferable. As the anionic surfactant, rosin acid soap, potassium oleate, sodium stearate,
Sodium myristate, sodium N-lauroyl sarcosinate, carboxylic acid salts such as di-potassium alkenyl succinate, sulfate salts such as sodium lauryl sulfate, sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate And phosphonates such as polyoxyethylene alkylphenyl ether sodium phosphate.

As a method for preparing an emulsion, a method of charging a monomer mixture in water and then adding a surfactant, a method of charging a surfactant in water and then adding a monomer mixture, Examples include a method of charging a monomer mixture with a surfactant and then adding water. Among them, a method of charging a monomer mixture in water and then adding a surfactant and a method of charging a surfactant in water and then charging a monomer mixture are methods for obtaining the multilayer structure polymer of the present invention. preferable.

The mixing device for preparing an emulsion prepared by mixing the monomer mixture which gives the innermost layer polymer (A) layer with water and a surfactant is a stirrer equipped with a stirring blade and Examples include various forced emulsification devices such as homogenizers and homomixers, and film emulsification devices.

The emulsion to be prepared is W / O
Type or O / W type dispersion structure can be used, but especially O / W type in which oil droplets of a monomer mixture are dispersed in water.
The diameter of the W-type dispersed phase oil droplets is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 15 μm or less. When it exceeds 100 μm, it is included in the obtained acrylic resin latex.
The number of giant polymer particles distributed in the range of up to 200 μm tends to increase.

The innermost layer polymer (A) layer, the crosslinked elastic polymer (B) layer, the intermediate layer (D) layer and the outermost layer layer which constitute the preferred multilayer structure polymer used in the production of the acrylic resin film of the present invention. As the polymerization initiator used when forming the combined (C) layer, known polymerization initiators can be used, and the addition method thereof can be a method of adding to either or both of the aqueous phase and the monomer phase. . Examples of particularly preferable initiators include peroxides, azo type initiators, and redox type initiators in which an oxidizing agent and a reducing agent are combined. Among these, a redox type initiator is more preferable, and a sulfoxylate type initiator in which ferrous sulfate / ethylenediaminetetraacetic acid disodium salt / Rongalite / hydroperoxide is combined is particularly preferable.

In particular, a monomer or a monomer mixture which gives the above-mentioned innermost layer polymer (A) layer, crosslinked elastic polymer (B) layer, intermediate layer (D) and outermost layer polymer (C), respectively. In the method of sequentially supplying to the reactor and polymerizing, after heating an aqueous solution containing ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalit to the polymerization temperature, the innermost layer polymer (A) is supplied to the reactor. To obtain a crosslinked elastic polymer (B) layer containing a polymerization initiator such as a peroxide, an intermediate layer (D) and an outermost layer polymer (C). The method of polymerizing is most preferable as the method of obtaining the multilayer structure polymer used in the present invention.

The multilayer structure polymer preferable as a raw material for the acrylic resin film of the present invention can be produced by recovering the multilayer structure polymer from the polymer latex produced by the above-mentioned method. The method for recovering the multi-layered polymer from the polymer latex is not particularly limited, but a method such as salting-out or acid-precipitating coagulation, spray-drying, freeze-drying, etc. may be mentioned and it is recovered in powder form.

As the surfactant to be added when molding the acrylic resin film of the present invention, known surfactants can be used, and a surfactant containing an alkyl sulfonate is preferable, and dioctyl sodium sulfosuccinate. A surfactant containing is more preferable from the viewpoint of roll releasability of the acrylic resin film.

The surfactant added when molding the acrylic resin film of the present invention may be added when pelletizing or may be added when molding the film, but the film is molded. It is more preferable to add it at this time. Addition during film formation is advantageous in terms of releasability from a heating roll during lamination and thermal stability of the surfactant. When a surfactant is added during pelletization, it is subjected to a large amount of heat history, which may accelerate the deterioration of the acrylic resin due to heat, which may cause fish eyes and the like, and also reduce the effect of roll peelability. Sometimes. The blending amount of the surfactant during film formation is preferably in the range of 0.05 to 10 parts by mass with respect to 100 parts by mass of the acrylic resin (I). If the content of the surfactant is less than 0.05 parts by mass, the releasability from the laminating roll is poor, and if it exceeds 10 parts by mass, the appearance of the film deteriorates, which is not preferable. A more preferable range of use is from the viewpoint of peelability from a laminating roll and good appearance, and
1 to 5 parts by mass.

The linear polymer (II) contained in the acrylic resin film of the present invention is not particularly limited, but (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, Examples of the linear polymer include a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, an acrylic acid alkyl ester, and another copolymerizable vinyl monomer. For example, acrylic acid hydroxyalkyl ester or / And 1 to 80 mass% of methacrylic acid hydroxyalkyl ester, 10 to 99 mass% of methacrylic acid alkyl ester, 0 to 79 mass% of acrylic acid alkyl ester, and 0 to 50 mass% of other copolymerizable vinyl monomer. %, The intrinsic viscosity is in the range of 0.3 L / g or less, and it is insoluble in chloroform. Those having a hydroxyl group containing no like.

Acrylic hydroxyalkyl ester and / or methacrylic acid hydroxyalkyl ester used in the linear polymer (II) having a hydroxyl group include
2-hydroxyethyl methacrylate, 2-methacrylic acid
Hydroxypropyl, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and the like are included. Among these, 2-hydroxyethyl methacrylate is particularly preferable.

Acrylic acid hydroxyalkyl ester,
Or / and the content in the linear polymer (II) having a hydroxy group of methacrylic acid hydroxyalkyl ester is 1 to
It is in the range of 80% by mass. If it is less than 1% by mass, the effect of peeling from the laminating roll is insufficient. On the other hand, when it exceeds 80% by mass, the dispersibility of the particles is deteriorated, and when it is made into a film, there are undispersed particles and the appearance may be deteriorated. A preferable range of use is 5 to 50% by mass for peelability from a laminating roll and good appearance. More preferably, it is in the range of 10 to 40% by mass.

As the methacrylic acid alkyl ester,
Lower methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate are preferred, and methyl methacrylate is particularly preferred. The content of the methacrylic acid alkyl ester is preferably in the range of 10 to 99% by mass, more preferably 30 to 90% by mass.

79% by mass of alkyl acrylate
Preferably contained in the range up to, specifically, methyl acrylate, ethyl acrylate, butyl acrylate,
Lower acrylic acid alkyl esters such as 2-ethylhexyl acrylate are preferred. The acrylic acid alkyl ester is preferably contained in the range of 0.5 to 40 mass%. More preferably, it is 5 to 25 mass%.

It is preferable that the linear polymer (II) having a hydroxyl group does not contain a component insoluble in chloroform.
A component insoluble in chloroform remains as an unmelted core when an acrylic resin film is formed, which causes a poor appearance. Specifically, the intrinsic viscosity and the molecular weight distribution Mw /
Mn (Mw is the weight average molecular weight, Mn is the number average molecular weight),
Carets and the like generated during the polymerization are important.

The intrinsic viscosity of the linear polymer (II) having a hydroxyl group is preferably adjusted to 0.3 L / g or less, and the linear polymer (II) having an unmelted hydroxyl group in the acrylic resin film ( It is necessary to reduce II).

The smaller the intrinsic viscosity, the better the dispersibility of the linear polymer (II) having a hydroxyl group in the acrylic resin film, and therefore the linear polymer (II) having a hydroxyl group that causes poor appearance (II ) Is reduced. It is preferably adjusted to a range of 0.12 L / g or less, more preferably 0.06 L / g or less. A polymerization regulator such as mercaptan is used for the regulation. N- for mercaptan
Octyl mercaptan, n-dodecyl mercaptan, t
-Dodecyl mercaptan and the like are used, but the known ones are not particularly limited to these and can be used.

The method for producing the linear polymer (II) having a hydroxyl group used for producing the acrylic resin film of the present invention is not particularly limited, but suspension polymerization or emulsion polymerization is preferable.

As the suspension polymerization initiator, those used in ordinary suspension polymerization are used, and examples thereof include organic peroxides and azo compounds.

As the suspension stabilizer, known and generally used suspension stabilizers can be used, and examples thereof include an organic colloidal polymer substance, an inorganic colloidal polymer substance, inorganic fine particles and a combination of these with a surfactant. Among these, an organic dispersant that does not leave an insoluble component in the acrylic resin film in the linear polymer (II) having a hydroxyl group is preferable. Further, it is preferable that even an inorganic dispersant can be removed by a treatment after the polymerization because it does not adversely affect the appearance.

The suspension polymerization is usually carried out by suspending the monomers together with a polymerization initiator in the presence of a suspension stabilizer. In addition to this, a polymer soluble in a monomer may be dissolved in the monomer and used.

Post-treatment after suspension polymerization is important, and it is preferable to remove cullet, which is a component insoluble in chloroform and generated during polymerization, which causes poor film appearance, by sieving. For example, those not containing cullet of 300 μm or more, preferably those not containing cullet of 100 μm or more are used. It is more preferable not to include cullet of 100 μm or less from the viewpoint of the film appearance, but in this case, normal beads are also removed by sieving, resulting in a decrease in yield.

In order to efficiently remove the cullet by sieving without lowering the product yield, the linear polymer having a hydroxyl group preferably has an average particle size of 300 μm or less. More preferably, it is 200 μm or less.

The amount of the linear polymer (II) having a hydroxyl group thus obtained is preferably in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the acrylic resin (I). 0.1
If the amount is less than 30 parts by weight, the peelability from a sufficient laminating roll will be slightly decreased, and if the amount is more than 30 parts by weight, the processability during film forming will tend to be slightly decreased. In order to obtain good peelability, it is more preferably 0.5 part by mass or more.

When the linear polymer (II) having a hydroxyl group is used, the releasability from the preheating roll can be improved without lowering the physical properties such as elongation of the film. Therefore, even if necessary in-mold forming such as vacuum forming of the film in advance, the film is not broken and can be used favorably.

In the production of the acrylic resin film of the present invention, powder can be used as a raw material and the pellet production process can be omitted, so that the acrylic resin film can be produced at low cost.

In this case, the powder has an average particle size of 500 μm.
m or more is preferable. When the average particle size of the powder is less than 500 μm, the supply to the film forming machine is likely to be unstable and the film thickness unevenness is likely to occur. On the other hand, the upper limit of the average particle size of the powder is not particularly limited as long as it is a size that allows film formation. However, it is difficult to manufacture a powder having a large particle size. Further, it is possible to obtain large particles by sieving, but there is a problem that processing cost is high.

This average particle diameter is a value calculated by sieving for 30 minutes with an M-2 type micro electromagnetic vibrating sieve manufactured by Tsutsui Rikagaku Kikai Co., Ltd.

The thermoplastic polymer (III) used in the production of the acrylic resin film of the present invention is obtained by polymerizing methyl methacrylate and another monomer having a copolymerizable double bond, which is used if necessary. It is a thermoplastic polymer having a reduced viscosity (measured at 25 ° C. by dissolving 0.1 g of polymer in 100 ml of chloroform) of 0.2 to 2 l / g.

The thermoplastic polymer (III) is a component (processing aid) that plays an important role in film moldability. The reduced viscosity of this thermoplastic polymer is important. It is preferable that the reduced viscosity is 0.2 l / g or more from the viewpoint of film formability of the obtained acrylic resin film,
On the other hand, when the amount exceeds 2 l / g, the film moldability tends to decrease. Particularly preferred thermoplastic polymer (III)
Has a reduced viscosity in the range of 0.2 to 1.2 l / g.

In the thermoplastic polymer (III), the content of methyl methacrylate is preferably 50% by mass or more. This content is based on a total of 100% by mass of methyl methacrylate and another monomer having a double bond copolymerizable therewith.

When polymerizing methyl methacrylate to obtain the thermoplastic polymer (III), another monomer having a double bond can be copolymerized. When another monomer is used, its content is preferably 50% by mass or less. This content is based on a total of 100% by mass of methyl methacrylate and another monomer having a double bond copolymerizable therewith.

In the thermoplastic polymer (III) used for producing the acrylic resin film of the present invention, an aromatic vinyl compound, a vinyl cyan compound or the like should be used as the vinyl-based monomer copolymerizable with methyl methacrylate. You can Aromatic vinyl compounds include styrene and α-
Substituted styrene, nucleus-substituted styrene and derivatives thereof, for example, α-methylstyrene, chlorostyrene, vinyltoluene and the like can be mentioned.

Furthermore, examples of the vinyl cyan compound include acrylonitrile and methacrylonitrile.

The thermoplastic polymer (III) used in the production of the acrylic resin film of the present invention is preferably obtained by an emulsion polymerization method. Further, the method for collecting the emulsion latex of the thermoplastic polymer (III) is not particularly limited. Specific examples thereof include salting out or acidifying coagulation, or methods such as spray drying and freeze drying, which can be recovered in powder form.

The amount of the thermoplastic polymer (III) used in the production of the acrylic resin film of the present invention is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the acrylic resin (I). When the thermoplastic polymer (III) is less than 0.1 parts by mass, the effect of suppressing fisheye generation tends to be insufficient, and when it exceeds 20 parts by mass, the melt viscosity increases and the film moldability decreases. There is a tendency.

The method of supplying the thermoplastic polymer (III) used for producing the acrylic resin film of the present invention to a single-screw extruder equipped with a film forming machine is not particularly limited, and the thermoplastic polymer (III) is not limited. (III) may be quantitatively supplied to the single-screw extruder equipped with a film-forming machine together with the acrylic resin (I) which is a powder containing an acrylic resin as a main component and having an average particle diameter of 500 μm or more.

As a specific example of feeding the thermoplastic polymer (III) to a single-screw extruder equipped with a film-forming machine, the thermoplastic polymer (III) produced by emulsion polymerization or suspension polymerization is mainly used as an acrylic resin. A method of measuring, mixing, and supplying with an acrylic resin (I) which is a powder having an average particle diameter of 500 μm or more as a component, and a masterbatch pellet containing a thermoplastic polymer (III) is a powder having an average particle diameter of 500 μm or more. A method in which the acrylic resin (I) is weighed, mixed and supplied is given. Of these, especially thermoplastic polymers (III)
The method of using a masterbatch pellet containing the above as a raw material is a more preferable method because it is possible to suppress the occurrence of optical distortion of the obtained acrylic resin film. The optical distortion referred to here is a streak-like or annual ring-like fluctuation occurring on the film surface and inside the film. The optical distortion in acrylic resin film is, for example, “Technology and application of functional film”.
[CMC Inc., issued July 30, 1982] 1
As described on page 28, when the film is attached to a window glass and used as a window glass, it appears as a distortion of an image of the outside world seen through the glass, which is important from the viewpoint of external clarity. Generally, the optical distortion of a film is difficult to be evaluated numerically as described in the above document, but it can be evaluated by the magnitude of the distortion of an image of the outside world when the film is viewed from a specific angle.

The masterbatch pellets can be produced by kneading and extruding the thermoplastic polymer (III) and the acrylic resin (I). A single-screw extruder or a twin-screw extruder can be usually used for kneading and extrusion. The content of the thermoplastic polymer (III) in the masterbatch pellets is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the acrylic resin (I). When the amount of the thermoplastic polymer (III) is less than 0.1 parts by mass, the thermoplastic polymer (II in the acrylic resin film obtained by the method of using a master batch pellet containing the thermoplastic polymer (III) as a raw material (II
Since the amount of I) becomes insufficient, the film moldability tends to decrease, and when it exceeds 30 parts by mass, the melt viscosity increases and the kneadability of the masterbatch pellets decreases, which is used as a raw material. The resulting acrylic resin film tends to have a poor appearance. The acrylic resin used for producing the masterbatch pellets is not particularly limited, but the above-mentioned acrylic resin used for producing the acrylic resin film is preferably used. Further, in the master batch pellets, a compounding agent for imparting various properties to the acrylic resin film obtained by the method of the present invention, for example, a stabilizer, an ultraviolet absorber, a processing aid, a plasticizer,
Impact resistance aids, foaming agents, fillers, colorants, matting agents, release agents, antibacterial agents and the like can be added.

The amount of the masterbatch pellets used is not particularly limited, but is preferably 1 part by mass or more per 100 parts by mass of the acrylic resin (I). When the amount of the pellet obtained by kneading and extruding the thermoplastic polymer (III) and the acrylic resin (I) which is a powder having an average particle size of 500 μm or more is less than 1 part by mass, the acrylic resin film tends to have optical distortion. . It is more preferably 5 parts by mass or more, and further preferably 7 parts by mass or more.

Further, when the compounding amount of the masterbatch pellets is large, there is a drawback that both the cost and the energy required for shaping become large. Therefore, it is desirable to reduce the amount as much as possible.

When the acrylic resin (I), which is a powder having an average particle diameter of 500 μm or more, is used to form a film, it is desirable to dry this powder with a drier to a water content of 0.3% or less. The acrylic resin (I) has hygroscopicity, and when the water content exceeds 0.3%, defects such as foaming, generation of eye drops and die lines tend to occur during film production. The moisture content of the powder is a value calculated by heating 10 g of the powder at 120 ° C. until a constant weight is reached and reducing the mass.

The drying method is not particularly limited, and examples thereof include dehumidified air drying, hot air drying, vacuum drying, and electromagnetic wave drying. Of the above-mentioned drying methods, the drying methods other than the dehumidifying air drying are usually batch drying methods using a plurality of dryers, and therefore continuous drying is difficult. On the other hand, dehumidified air drying is advantageous for continuous production because it can be dried continuously, and is preferable in terms of equipment space, equipment cost, and the like.
Further, it is preferable to install a rotary valve or a bridge breaker in the discharge part of the dryer.

By the drying process as described above, the water content of the acrylic resin (I), which is a powder containing an acrylic resin as a main component and having an average particle size of 500 μm or more, is reduced to 0.3% or less, and the acrylic resin (I) is manufactured. The mixture is fed to a single-screw extruder equipped with a membrane machine, kneaded, and extruded to form a film.

The thickness of the acrylic resin film of the present invention is not particularly limited, but preferably 10 to 500.
μm. When the thickness is 10 to 500 μm, the rigidity becomes appropriate, so that the laminating property, the secondary workability and the like become easy. Further, the film-forming property is stable and the film can be easily manufactured. The thickness is more preferably 15 μm to 200 μm, further preferably 40 μm to 200 μm.

The method for molding the acrylic resin film of the present invention is not particularly limited, and known methods such as solution casting method, T-die method and inflation method such as melt extrusion method can be used. Among them, the T-die method is the most preferable method from the viewpoint of economy.

The heat distortion temperature (measured according to ASTM D648) of the acrylic resin film of the present invention is preferably 70 ° C. or higher. When the heat distortion temperature is 70 ° C. or higher, the surface roughness of the laminate having the film on the surface after heating is less likely to occur. Further, when the heat distortion temperature is 80 ° C. or higher, for example, when the laminate having the film surface roughened by embossing or the like is heat-processed, it is possible to suppress the deterioration of the design property due to the luster of the embossed surface, The industrial value is high when the acrylic resin film is used for such an application.

In the acrylic resin film of the present invention, if necessary, general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers,
Antibacterial agents, antifungal agents, foaming agents, release agents, antistatic agents, coloring agents, matting agents, ultraviolet absorbers and the like can be included. Particularly, from the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. The molecular weight of the ultraviolet absorber used is preferably 300 or more, and particularly preferably 400 or more. If an ultraviolet absorber having a molecular weight of less than 300 is used, it may be volatilized on a transfer roll or the like during the production of the film, resulting in roll contamination. The type of the ultraviolet absorber is not particularly limited, but it is a benzotriazole type having a molecular weight of 400 or more or a molecular weight of 4 or more.
A triazine-based compound of 00 or more can be particularly preferably used. Specific examples of the former include Tinuvin 234 manufactured by Ciba Geigy, Adeka Stab LA-31 manufactured by Asahi Denka Co., Ltd., and specific examples of the latter include Tinuvin 1577 manufactured by Ciba Geigy.
Etc.

As the method for adding the compounding agent, a method of supplying the compounding agent together with the acrylic resin to a film forming machine for forming a film using the acrylic resin, and a mixture of the compounding agent previously added to the acrylic resin to various kneading machines are used. There is a method of kneading and mixing. Examples of the kneader used in the latter method include a normal single-screw extruder, a twin-screw extruder, a Banbury mixer, and a roll kneader.

By laminating the acrylic resin film of the present invention on the surface of a base material such as various resin molded products, wood products and metal molded products, a laminate having the acrylic resin film on the surface can be produced.

The acrylic resin film of the present invention may be used by printing by a suitable printing method, if necessary, in order to impart design properties to various base materials. In this case, it is preferable to use an acrylic resin film that has been subjected to one-sided printing treatment, and it is preferable to arrange the printing surface on the adhesive surface to the base resin from the viewpoint of protecting the printing surface and imparting a high-class feeling. Further, when the color tone of the base material is utilized and it is used as a substitute for transparent coating, it can be used as it is as it is. In particular, for the purpose of utilizing the color tone of the substrate as described above, the acrylic resin film of the present invention is superior in transparency, depth feeling and high quality feeling to the polyvinyl chloride film and the polyester film.

If necessary, a film having a matte treatment such as embossing or a coloring treatment may be used.

The acrylic resin film of the present invention can be laminated on a thermoplastic resin film or sheet.
Examples of the thermoplastic resin film or sheet include ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or resins containing these as main components.
From the viewpoint of adhesiveness, an ABS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin or a resin sheet containing these resins as a main component is preferable. However, it is possible to bond the acrylic resin film of the present invention to the substrate by using an adhesive layer even with a substrate resin such as a polyolefin resin sheet which is not heat-fused.

The acrylic resin film or the acrylic resin film laminated sheet of the present invention can be used by being stuck to various resin molded products, woodwork products and metal molded products. As a method for laminating the laminated sheet to the base material, a method using an adhesive, a method by an adhesive processing, a thermal laminating method, a laminated sheet or a member preliminarily formed of the laminated sheet at the time of injection molding is inserted into a mold and molded. In-mold molding method and the like.

Among the resin molded products, examples of the thermoplastic resin molded products which can be melt-bonded to the acrylic resin film of the present invention include the above resins.

As a method for producing a laminate having the acrylic resin film of the present invention on its surface, in the case of forming a laminate having a two-dimensional shape, a known method such as heat lamination may be applied to a heat-bondable substrate. Can be used. Further, it is possible to bond the base material which is not heat-sealed via an adhesive.

On the other hand, in the case of molding into a three-dimensional laminated body, an insert molding method in which a preformed acrylic resin film is inserted into a mold for injection molding, or an in-mold in which injection molding is performed after vacuum molding in the mold A known molding method such as a molding method can be used. In the in-mold molding method, after heating the film, vacuum molding is performed in a mold having a vacuuming function. This method is preferable from the viewpoints of workability and economy because the film molding and injection molding can be performed in one step. The heating temperature is preferably equal to or higher than the softening temperature of the acrylic resin film. This depends on the thermal properties of the film or the shape of the molded product, but usually 70
℃ or above. Further, if the temperature is too high, the surface appearance may be deteriorated or the releasability may be deteriorated. This also depends on the thermal properties of the film or the shape of the molded product, but is usually preferably 170 ° C. or lower.

In the in-mold molding method, after the three-dimensional shape is imparted by vacuum molding in this way, the acrylic resin film and the base resin are melt-integrated by injection molding to form an acrylic laminate molding having an acrylic resin film layer on the surface layer. You can get the goods.

The acrylic resin film of the present invention or the laminate having the acrylic resin film on the surface may be subjected to surface treatment for imparting various functions, if necessary, to the surface of the acrylic resin film. As surface treatment for imparting functions, printing treatment such as silk printing or ink jet printing, metal deposition for imparting metal tone or antireflection, sputtering, wet plating treatment, surface hardening treatment for improving surface hardness, stain prevention Water repellent treatment or photocatalyst layer forming treatment, antistatic treatment for the purpose of dust adhesion prevention or electromagnetic wave cutting, antireflection layer formation, antiglare treatment and the like.

Industrial applications of the acrylic resin film or laminated sheet of the present invention include window frames, door materials, decorative steel sheets, wall materials, furniture, wallpaper and other construction sheets, home appliance housing skin materials, vehicle interior skin materials, etc. The above-mentioned various industrial products can be used as a coating material for the purpose of imparting a design property to a base material and protecting the base material.

[0095]

The present invention will be described with reference to the following examples.

In the examples and comparative examples, "part" means "part by mass" and "%" means "% by mass". The abbreviations in Reference Examples are as follows.

Methyl methacrylate MMA butyl acrylate BA methyl acrylate MA hydroxyethyl methacrylate HEMA allyl methacrylate AMA 1.3-butylene glycol dimethacrylate 1.3BD t-butyl hydroperoxide tBH cumene hydroperoxide CHP lauryl peroxide LPO n-octyl mercaptan nOM emulsifier. (1): Partially neutralized sodium hydroxide of a mixture of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid [trade name: phosphanol LO52
9, manufactured by Toho Kagaku Co., Ltd.] Preparation Example 1: Production of multi-layer structure polymer (I-1) latex 195 parts of ion-exchanged water was put into a polymerization vessel equipped with a condenser, the temperature was raised to 70 ° C, and further, A mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was added all at once. Then, with stirring under nitrogen, 0.3 parts of MMA, 4.5 parts of BA, BD
A monomer mixture consisting of 0.2 part, AMA 0.05 part, and CHP 0.025 part and a mixture consisting of 1.3 parts of emulsifier (1) were added dropwise to the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes. The polymerization of the innermost layer polymer (A-4) was completed. Next, MMA1.5 part, BA22.5 part, BD1.
CHP with a monomer mixture consisting of 0 part and 0.25 part of AMA.
After adding together with 0.016 parts for 90 minutes, the reaction was continued for 60 minutes to obtain a two-layer crosslinked rubber elastic body containing the crosslinked elastic polymer (B-4).

Subsequently, 6 parts of MMA, 4 parts of BA, and AMA
A mixture of 0.075 parts and CHP 0.0125 parts was added to 4 parts.
After dropping into the polymerization container over 5 minutes, the reaction was continued for 60 minutes to form an intermediate layer (D-4).

Next, 55.2 parts of MMA and 4.8 of BA
Part, n-OM 0.19 part, and t-BH 0.08 part were added dropwise to the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes to give the outermost layer polymer (C-
4) was formed to obtain a polymer latex of the multilayer structure polymer (I-1).

Preparation Example 2: Production of Multilayer Structure Polymer (I-2) Latex After charging 8.5 parts of ion-exchanged water in a container equipped with a stirrer, 0.3 part of MMA, 4.5 parts of BA, and 0.2 of BD. Division, A
A monomer mixture consisting of 0.05 part of MA and 0.025 part of CHP was added and mixed with stirring. Then emulsifier (1) 1.3
Part was put into the above container while stirring, and stirring was continued for 20 minutes again to prepare an emulsion (N-1). The average particle size of the dispersed phase in the obtained emulsion was 10 μm.

Next, 186.5 parts of ion-exchanged water was placed in a polymerization vessel equipped with a condenser and the temperature was raised to 70 ° C. Further, 5 parts of ion-exchanged water was charged with 0.20 part of sodium formaldehyde sulfoxylate. Ferrous sulfate 0.0001 parts, EDT
The mixture prepared by adding 0.0003 parts of A was added all at once. Then, while stirring under nitrogen, the emulsion (N-1)
Was dropped into the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the innermost layer polymer (A-1).
Next, MMA1.5 part, BA22.5 part, BD1.0
Part, a monomer mixture consisting of 0.25 parts of AMA.
After adding together with 016 parts for 90 minutes, the reaction was continued for 60 minutes to obtain a two-layer crosslinked rubber elastic body containing the crosslinked elastic polymer (B-1).

Subsequently, 6 parts of MMA, 4 parts of BA, and AMA
A mixture of 0.075 parts and CHP 0.0125 parts was added to 4 parts.
After adding dropwise to the polymerization container over 5 minutes, the reaction was continued for 60 minutes to form an intermediate layer (D-1).

Next, 55.2 parts of MMA and 4.8 of BA
Part, n-OM 0.19 part, and t-BH 0.08 part were added dropwise to the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes to give the outermost layer polymer (C-
1) was formed to obtain a polymer latex of the multilayer structure polymer (I-2).

Preparation Example 3: Production of Linear Polymer (II) Having Hydroxyl Group The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet and the like.

MA 10 parts by mass MMA 60 parts by mass HEMA 30 parts by mass n-OM 0.08 parts by mass LPO 0.5 parts by mass MMA / methacrylate / ethyl methacrylate sulfonate copolymer 0.05 parts by mass Sodium sulphate 0.5 parts by mass Ion-exchanged water 250 parts by mass After the inside of the container was sufficiently replaced with nitrogen gas, the mixture of the above mixture was heated to 75 ° C. with stirring, and polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C and further 4
Polymerization was completed by holding the mixture for 5 minutes, followed by sieving under the conditions of a mesh size of 150 mesh, and the passed beads were dehydrated and dried to obtain a linear polymer (II) having a hydroxyl group.

The intrinsic viscosity of this polymer measured by the following method was 0.11 L / g, Mw / Mn was 1.9, and the average particle size was 70 μm.

(Intrinsic Viscosity of Linear Polymer Having Hydroxyl Group) Intrinsic viscosity and reduced viscosity were measured by AVL manufactured by Sun Denshi Kogyo.
-2C It measured at 25 degreeC using chloroform as a solvent using an automatic viscometer. In the measurement of reduced viscosity, a sample prepared by dissolving 0.1 g of the sample in 100 ml of chloroform was used.

(Measurement of Dispersion Ratio (Mw / Mn) of Linear Polymer Having Hydroxyl Group) Shimadzu LC-6A system (manufactured by Shimadzu Corporation) was used and KF-8 was used as a GPC column.
02.5, KF-804, KF-805 (manufactured by Showa Denko)
The measurement was carried out in terms of polystyrene by using three connected ones and using THF as a solvent.

(Average Particle Diameter of Linear Polymer Having Hydroxyl Group) The average particle diameter of the obtained polymer having a hydroxyl group is H
The measurement was performed using a laser diffraction / scattering particle size distribution analyzer LA-910 manufactured by ORIBA Ltd.

The heating roll peelability was measured by the following method.

<Peelability Test Method for Mirror Surface Single Roll> 40
The acrylic resin film was rotated at a speed of 5 rpm while being brought into contact with the φ mirror surface roll, and the acrylic resin film was taken out from the mirror surface in the vertical direction. The heating temperature of the mirror surface roll at this time was 140 ° C., and the contact between the film and the mirror surface roll was set to be 1/2 of the circumference of the mirror surface roll.

The film was taken out under the above conditions for 30 minutes, and the film in which the acrylic resin film was not taken up by the roll was marked with ◯, and the film when the acrylic resin film was wound around the roll without being peeled from the roll was marked with x.

<Peeling Test Method for Embossing Roll> The acrylic resin film was sandwiched between the embossing roll and the mirror surface roll, and the acrylic resin film was wound on the downstream side of each roll. The heating temperature of the embossing rolls at this time was 140 ° C, and the pressure when sandwiched between the rolls was 4.9M.
It was Pa.

The film was taken out under the above conditions for 30 minutes, and the film in which the acrylic resin film was not taken up by the roll was marked with ◯, and the film when the acrylic resin film was wound around the roll without being peeled from the roll was marked with x.

Example 1 The acrylic resin latex obtained in Preparation Example 1 was filtered through a filter having an opening of 75 μm, salted out and dehydrated, and washed with water to obtain a wetted powder of a multilayer structure polymer.

Then, the powdery multilayer structure polymer was mixed with 3
Using a 5 mmφ screw type twin-screw extruder (L / D = 26), it was squeezed and dehydrated at a cylinder temperature of 190 to 210 ° C. to obtain granule powder having an average particle diameter of 650 μm. 10 the granulated powder
0 parts, 0.5 parts of aerosol OT-B (trade name, components: sodium dioctyl succinate = 85%, sodium benzoate = 15%) manufactured by Mitsui Cytec Co., Ltd. as a surfactant were obtained in Preparation Example 3. As a thermoplastic polymer (III), 1 part of the linear polymer (II) having a hydroxyl group thus obtained, Metabrene P-530A (trade name, manufactured by Mitsubishi Rayon Co., Ltd.)
1 part of reduced viscosity: 0.375 l / g), 1.5 parts of TINUVIN P (trade name) manufactured by Ciba-Geigy Co., Ltd. as an ultraviolet absorber, ADEKA STAB AO-50 manufactured by Asahi Denka Co., Ltd.
0.1 parts of (trade name) and 0.8 parts of Metabrene L-1000 (trade name) manufactured by Mitsubishi Rayon Co., Ltd. were used and mixed by an automatic weighing and mixing apparatus [Tamaki Co., Ltd., auto blender].

Then, using a 40 mmφ screw type extruder (L / D = 26), the cylinder temperature was 200 to 26.
The mixture was melt-kneaded and pelletized at 0 ° C and a die temperature of 250 ° C.
The pellets were dried at 80 ° C. for a whole day and night, and formed into a film having a thickness of 0.05 mm by using a T-die with a 115 mmφ extruder to obtain an acrylic resin film of the present invention.

Table 1 shows the evaluation results of the film surface gloss, peel strength and roll peelability.

<Example 2> Granules of a multi-layered polymer having an average particle diameter of 650 µm were obtained in the same manner as in Example 1 except that the acrylic resin latex obtained in Preparation Example 2 was used.
Furthermore, an acrylic resin film was obtained in the same manner as in Example 1 by using the granular powder.

Table 1 shows the evaluation results of the film surface gloss, peel strength and roll peelability.

<Example 3> 100 parts of the granular powder used in Example 1, 1 part of the linear polymer (II) having a hydroxyl group obtained in Preparation Example 3, 1 part of Metablen P-530A, ADEKA STAB AO-50 0.1 part, Metabrene L-10
Using 0.8 parts of 00, 40 by mixing with an automatic weighing and mixing device,
Using a mmφ twin-screw extruder (L / D = 26), the mixture was melt-kneaded and pelletized at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C.

100 parts of the pellet, 1.5 parts of TINUVIN P as an ultraviolet absorber and 0.5 parts of aerosol OT-B.
Parts and blended with a 115 mmφ extruder using a T-die to 0.0
It was molded into a film having a thickness of 5 mm to obtain the acrylic resin film of the present invention.

Table 1 shows the evaluation results of the film surface gloss, peel strength and roll peelability.

<Example 4> An acrylic resin film was obtained in the same manner as in Example 1 except that 3 parts of the aerosol OT-B was used.

Table 1 shows the evaluation results of the film surface gloss, peel strength, and roll peelability.

Example 5 100 parts of the granular powder produced in Example 1, 0.5 part of Aerosol OT-B, 1 part of the linear polymer (II) having a hydroxyl group obtained in Preparation Example 3 were prepared. Part, Metabrene P-530A 1 part, Tinuvin P 1.5 parts,
ADEKA STAB AO-50 0.1 part, Metabrene L-1
0.8 parts of 000 were mixed in an automatic metering mixer.

This mixture was molded into a film having a thickness of 0.05 mm by a T-die with a 115 mmφ extruder to obtain an acrylic resin film of the present invention.

Table 1 shows the evaluation results of the surface gloss, peel strength and roll peelability of the film.

<Example 6> 100 parts of the granular powder produced in Example 1 and 5 parts of the linear polymer (II) obtained in Preparation Example 3 were used.
Part, Metabrene P-530A 5 parts, AO-50 0.
5 parts, 4 parts of Metabrene L-1000 were mixed by an automatic metering and mixing device [and a cylinder temperature of 200 to 26 was obtained using a 40 mmφ screw type extruder (L / D = 26).
The mixture was melt-kneaded and pelletized at 0 ° C and a die temperature of 250 ° C.

20 parts of the pellets, 80 parts of the granular powder produced in Example 1, 0.5 parts of aerosol OT-B and 1.5 parts of TINUVIN P were blended, and a T-die was used with a 115 mmφ extruder. It was molded into a film having a thickness of 0.05 mm to obtain the acrylic resin film of the present invention.

Table 1 shows the evaluation results of the film surface gloss, peel strength and roll peelability.

<Example 7> An acrylic resin film was obtained in the same manner as in Example 6 except that 25 parts of the linear polymer (II) obtained in Preparation Example 3 was used.

Table 1 shows the evaluation results of the film surface gloss, peel strength, and roll peelability.

<Comparative Example 1> An acrylic resin film was obtained in the same manner as in Example 1 except that the aerosol OT-B was not used.

Table 1 shows the evaluation results of the film surface gloss, peel strength and roll peelability.

Comparative Example 2 Aerosol OT-B was added to 0.0
An acrylic resin film was obtained in the same manner as in Example 1 except that 5 parts were used.

Table 1 shows the evaluation results of the film surface gloss, peel strength and roll peelability.

<Comparative Example 3> An acrylic resin film was obtained in the same manner as in Comparative Example 1 except that 35 parts of the linear polymer (II) obtained in Preparation Example 3 was used. The resulting acrylic resin film had many fish eyes and had a poor appearance.

Table 1 shows the evaluation results of the film surface gloss, peel strength and roll peelability.

Comparative Example 4 An acrylic resin film was obtained in the same manner as in Example 1 except that the linear polymer (II) obtained in Preparation Example 3 was not used.

Table 1 shows the evaluation results of the film surface gloss, peel strength and roll peelability.

[0142]

[Table 1]

As described above, according to the present invention,
Without impairing the original features of the acrylic resin film,
An acrylic resin film having excellent releasability from a heating roll during heat lamination, a method for producing the same, and a laminated sheet obtained by laminating the same can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 265/06 C08F 265/06 C08K 5/00 C08K 5/00 C08L 33/06 C08L 33/06 33/12 33/12 51/00 51/00 F-term (reference) 4F071 AA22X AA31X AA32X AA33X AA76 AA77 AE10 AF19Y AF30 AF32Y AF53 BB06 BC01 4F100 AK01A AK01B AK25A AK25J J01J01J01J01J16BJA16 J14B16A16J17B16A16A17A17X JN21A YY00A 4J002 BB12W BG04X BG05X BG06Y FD316 GL00 GN00 GQ00 4J026 AA45 BA25 BA27 BA28 BA34 BA35 BA36 FA07 4J100 AB02Q AB02R AJ02Q AJ02R AL02P AL03P AL03Q AL03R AL04P AL05Q AL09P AL62R AM02Q AM02R AM15Q AM15R CA04 CA05 CA06 CA23 CA29 JA43 JA67

Claims (5)

[Claims] 1. A film cut out to a diameter of 10 mm is sandwiched between metal plates having a surface roughness of # 250 and pressed at 170 ° C. for 8 minutes under a load of 7 kg, and then the metal plate is peeled in the vertical direction. The peel strength is 30 kgf or less,
An acrylic resin film having a surface gloss of 80 to 120%. 2. The method for producing an acrylic resin film according to claim 1, wherein a surfactant is added to the acrylic resin (I), and then the acrylic resin (I) is molded into a film. 3. A (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, having 1 carbon atom.
The acrylic resin according to claim 1, which contains a linear polymer (II) having a hydroxyl group, which is composed of an alkyl methacrylate having an alkyl group of 4 to 4, an alkyl ester of acrylic acid and another vinyl monomer copolymerizable therewith. the film. 4. A raw material comprising an acrylic resin (I) which is a powder having an average particle diameter of 500 μm or more and the following thermoplastic polymer (III) is fed to an extruder, kneaded and extruded to form a film. The method for producing an acrylic resin film according to claim 1, wherein: Thermoplastic polymer (III) Methyl methacrylate and other vinylic monomer copolymerizable with it. Reduced viscosity of the obtained polymer (polymer 0.1 g is dissolved in chloroform 100 ml, 25 ° C
The polymer) is 0.2 to 2 L / g. 5. An acrylic resin film laminated sheet obtained by laminating the acrylic resin film according to claim 1 on a thermoplastic resin film or sheet.