JP4798678B2 - Acrylic resin film and laminate using the same - Google Patents

Description

実施例および比較例より、次のことが明らかとなった。
【０１１３】
１）実施例１〜４のアクリル樹脂フィルム（Ｆ−１〜４）は、いずれも良好な製膜性、透明性、表面光沢と良好な溶剤に接触した後の機械特性の保持性および良好な耐アルコール性を示す。特に実施例１および２のアクリル樹脂フィルム（Ｆ−１および２）の溶剤に接触した後の機械特性の保持性と耐アルコール性のバランスは従来知られているアクリル樹脂フィルムにはない高いレベルであり、このように耐溶剤性に優れたアクリル樹脂フィルムの工業的利用価値は高い。
【０１１４】
２）比較例４および５のアクリル樹脂フィルムは、いずれも製膜性が不良であり、５０μｍ厚みの膜厚が均一なフィルムを得ることができず、フィルムおよびこれを用いた積層体の評価が不能であった。
【０１１５】
３）比較例１および３のゴム含有重合体（Ｃ）を含有しないアクリル樹脂フィルム（Ｇ−１および３）は、いずれも製膜性、表面光沢および溶剤に接触した後の機械特性の保持性は良好なものの、耐アルコール性が不良であり、これを表面に使用した積層体がアルコールと接触した場合に白化等の変色が発生し、このように外観変化が生じるアクリル樹脂フィルム積層体は、使用できる用途が限られるため、工業的利用価値が低い。
【０１１６】
また、比較例１および３のゴム含有重合体（Ｃ）を含有しないアクリル樹脂フィルム（Ｇ−１および３）は、いずれも５０μｍでの曇価が高く、高いレベルの意匠性、とりわけ積層体表面に深み感のある透明性が必要となる用途に使用することができない。
【０１１７】
４） 比較例２のゴム含有重合体（Ｂ）を含有しないアクリル樹脂フィルム（Ｇ−２）は、製膜性、透明性、表面光沢および耐アルコール性は良好なものの、溶剤に接触した後の機械特性が著しく低下し、例えば印刷、表面処理等溶剤を含む処理液と接触した場合、フィルムの強度が低下し、取り扱い性を損なうといった不都合が生じ、このように耐溶剤性に劣るアクリル樹脂フィルムは、使用できる用途が限られるため工業的利用価値が低い。
【０１１８】
【発明の効果】
本発明は以上説明した通りであり、次のように特別に顕著な効果を奏し、その産業上の利用価値は極めて大である。
【０１１９】
１）本発明のアクリル樹脂フィルムは製膜性、透明性、表面光沢、表面硬度、および耐溶剤性に優れる。
【０１２０】
２）特に溶剤に接触した後の機械特性の保持性とこれを表面に有する積層体の耐アルコール性のバランスは、従来知られているアクリル樹脂フィルムでは得られない非常に高いレベルであり、各種工業材料とりわけ積層用フィルム材料としての利用価値は極めて高い。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an acrylic resin film excellent in solvent resistance, transparency, surface hardness and design.
[0002]
[Prior art]
Acrylic resin films made of acrylic resin containing rubber are laminated on the surface of various resin molded products, woodwork products, and metal molded products, taking advantage of their excellent transparency, weather resistance, flexibility, and workability. It is used as a covering material for building materials such as furniture, door materials, window frames, baseboards, and bathroom interiors, marking films, and high-intensity reflector coating films.
[0003]
In addition, the acrylic resin film can be printed and laminated on various substrates to enhance the design of the substrate surface. This application is widely used for decorating the substrate surface as an alternative coating technology. Yes.
[0004]
Conventionally, as an acrylic resin film used by laminating on the surface of the substrate in this way, JP-A 63-77963 discloses transparency with an acrylic resin containing a specific rubber-containing polymer as a component of the film, An acrylic resin film excellent in weather resistance is disclosed. In addition, acrylic resin films having good surface hardness, deep transparency, and good printability suitable for the above-described application for paint replacement are described in JP-A-8-323934 and JP-A-10-279766. Has been.
[0005]
On the other hand, in recent years, the use field of the acrylic resin film laminated on the surface of the base material is diverse, and uses that require solvent resistance as a surface protection of the base material are increasing.
[0006]
Applications in which such solvent resistance is particularly important, or methods for using acrylic resin films include, for example, resistance to alcohol components contained in fragrances when laminated on vehicle interior horizontal parts, films for coating high-intensity reflectors, etc. Resistance to ketones, alcohols, and aromatic hydrocarbons contained in silk printing ink applied to the film surface when used as, or when imparting a photocatalytic function to various building materials and high-intensity reflective materials on the surface For example, resistance to ketones, alcohols and aromatic hydrocarbons contained in the treatment liquid applied on the surface of the film for forming the photocatalyst layer may be mentioned.
[0007]
The resistance to the solvent in the above use or the usage method of the acrylic resin film is important that there is little change in the appearance of the film due to contact with the solvent, especially the film surface discoloration, crack generation, dissolution, etc. due to contact with the solvent. Less is important.
[0008]
Conventionally, the above-mentioned JP-A-63-77963, JP-A-8-323934, JP-A-10-279766, etc., which have been proposed as acrylic resin films used for substrate protection, There is no description regarding the solvent resistance, and the acrylic resin films described in the examples of the respective publications have a large resistance to solvent, particularly white discoloration when contacted with alcohols. The large acrylic resin film has a restriction in its use as a film for protecting a substrate.
[0009]
On the other hand, as a method for improving the solvent resistance of an acrylic resin, JP-A-7-149994 discloses a method using an acrylic resin-based thermoplastic resin composition having a specific structure. Japanese Patent Application Laid-Open No. 11-60876 describes that a good solvent-resistant film can be obtained by using a specific elastic copolymer as a constituent of an acrylic resin film. Furthermore, Japanese Patent Application Laid-Open No. 2001-59048 discloses an anti-resistant composition comprising an acrylic copolymer containing a graft layer obtained by polymerizing a monomer mixture containing a vinyl cyanide monomer as a constituent of an acrylic resin film. An acrylic resin film is disclosed that has good solvent properties and is less susceptible to discoloration such as whitening and changes in appearance such as cracks when contacted with alcohols.
[0010]
However, although the method of JP-A-7-149994 is effective in suppressing the occurrence of cracks when it comes into contact with a solvent of a molded product having a relatively large thickness such as an injection molded product, this resin composition is used, for example, When used as a thin film of 200 μm or less, sufficient solvent resistance could not be obtained, and there was a limit to use as an acrylic resin film.
[0011]
In addition, the method described in JP-A-11-60876 describes the improvement of the mechanical properties of an acrylic resin film when contacted with a solvent by improving the solubility of the film in a good solvent such as toluene. However, there is no description about the suppression of whitening when it comes into contact with alcohols such as ethanol and isopropanol, and the acrylic resin film produced by the method of the example causes significant whitening when brought into contact with alcohols. As described above, the acrylic resin film that changes in appearance due to contact with alcohols is limited in use.
[0012]
On the other hand, an acrylic using an elastic copolymer including a graft layer obtained by polymerizing a monomer mixture containing a vinyl cyanide monomer described in JP-A-2001-59048 as a constituent of an acrylic resin film. The resin film improves the solubility of the film in good solvents such as toluene and can suppress changes in appearance such as whitening and cracks when contacted with alcohols such as ethanol and isopropanol. Since the graft layer of the rubber-containing polymer constituting the resin film contains a polymer of a monomer mixture containing a vinyl cyanide monomer, the acrylic resin film is colored yellow, and particularly has a thickness of 100 to 200 μm. It is used for applications that require a high degree of transparency and hue control due to the large yellow coloration when formed into a film-like product. It has been difficult to.
[0013]
That is, conventionally, no acrylic resin film has been found that has excellent transparency with little yellowing and suppresses changes in appearance such as whitening and cracks upon contact with alcohols such as ethanol and isopropanol. Development of technology that satisfies the above has been strongly desired.
[0014]
[Problems to be solved by the invention]
An object of the present invention is to provide an acrylic resin film having excellent solvent resistance and transparency.
[0015]
[Means for Solving the Problems]
The present invention resides in an acrylic resin film containing the following (A), (B) and (C) and a laminate using the same.
[0016]
Thermoplastic polymer (A)
It is composed of 50 to 100% by mass of methacrylic acid alkyl ester units, 0 to 50% by mass of acrylic acid alkyl ester units and 0 to 49% by mass of at least one unit of other vinyl monomers copolymerizable therewith. A thermoplastic polymer having a combined viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of 0.1 L / g or less.
[0017]
Rubber-containing polymer (B)
A rubber-containing polymer (B) comprising an elastic polymer ((B-1) + (B-2)) comprising a polymer (B-1) and a rubber polymer (B-2),
A polymer (B-1) whose innermost layer has a glass transition temperature of 0 to 25 ° C., the main component of which is a methacrylic acid alkyl ester or an acrylic acid alkyl ester;
A rubber polymer (B-2) having a glass transition temperature of less than 0 ° C. whose intermediate layer is mainly composed of alkyl acrylate ester,
The outermost layer polymer (B-3) whose outermost layer is mainly composed of alkyl methacrylate.
A rubber-containing polymer having a three-layer structure comprising a mass average particle diameter in the range of 0.2 to 0.4 μm.
[0018]
Rubber-containing polymer (C)
In the inner layer 1 Has a structure of two or more layers Both The polymer (C-1) is grafted with a hard polymer (C-2) having a structure of one layer or two or more layers in which the outer layer is a methacrylic acid alkyl ester as a main constituent of the polymer. Rubber-containing polymer having a multi-layer structure of layers or more and having a mass average particle diameter of less than 0.2 μm A rubber-containing polymer in which 35 to 100% by mass of an alkyl acrylate is used for obtaining the copolymer (C-1). .
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The thermoplastic polymer (A) constituting the acrylic resin film of the present invention comprises 50-100% by mass of methacrylic acid alkyl ester units, 0-50% by mass of acrylic acid alkyl ester units, and other vinyls copolymerizable therewith. It is composed of 0 to 49% by mass of at least one monomer unit, and the polymer has a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of 0.1 L / g or less. It is a coalescence.
[0020]
It is preferable that the reduced viscosity of the thermoplastic polymer (A) is 0.1 L / g or less because appropriate elongation occurs at the time of melting the film raw material resin and the film forming property is improved. Moreover, it is preferable that the reduced viscosity of a thermoplastic polymer (A) is 0.05 L / g or more. If it is higher than 0.05 L / g, the film is not brittle, and it is difficult to cause film breakage during film formation and printing.
[0021]
Examples of the alkyl methacrylate used for producing the thermoplastic polymer (A) include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. Among these, use of methyl methacrylate is most preferable. The methacrylic acid alkyl ester unit is contained in the thermoplastic polymer (I) in an amount of 50 to 100% by mass. Preferably it is 50-99.9 mass%.
[0022]
As the alkyl acrylate ester, methyl acrylate, ethyl acrylate, butyl acrylate or the like can be used. The acrylic acid alkyl ester unit is contained in the range of 0 to 50% by mass, preferably in the range of 0.1 to 40% by mass. Other copolymerizable vinyl monomers include aromatic alkenyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds, acid group-containing vinyl compounds such as methacrylic acid and itaconic acid, and N-cyclohexylmaleimide. Known monomers such as maleimide compounds such as N-phenylmaleimide can be used. These other copolymerizable vinyl monomer units are contained in the range of 0 to 49% by mass.
[0023]
Although the polymerization method of a thermoplastic polymer (A) is not specifically limited, It can carry out by methods, such as normal suspension polymerization, emulsion polymerization, and block polymerization. In addition, in order to make a viscosity into the range limited by this invention, it is necessary to use a chain transfer agent. Known chain transfer agents can be used, but mercaptans are preferred. The amount of the chain transfer agent needs to be appropriately determined depending on the type and composition of the monomer.
[0024]
The rubber-containing polymer (B) constituting the acrylic resin film of the present invention is a polymer whose innermost layer has a glass transition temperature of 0 ° C. or higher and lower than 25 ° C. whose main component is a methacrylic acid alkyl ester or an acrylic acid alkyl ester. (B-1), and the intermediate layer is a rubber polymer (B-2) having a glass transition temperature mainly composed of an alkyl acrylate ester and lower than 0 ° C., and the polymer (B-1) and the rubber The outermost layer polymer (B-3) mainly composed of alkyl methacrylate as the outermost layer is added to the elastic copolymer ((B-1) + (B-2)) made of the polymer (B-2). This is a polymer having a grafted three-layer structure and an average particle diameter in the range of 0.2 to 0.4 μm.
[0025]
As the alkyl acrylate ester used here, known ones can be used, and among them, butyl acrylate, -2-ethylhexyl acrylate and the like are preferable.
[0026]
As the alkyl methacrylate, known ones can be used, but methyl methacrylate, butyl methacrylate and the like are preferable.
[0027]
In obtaining the elastic copolymer, other known copolymerizable vinyl monomers can be copolymerized. As the vinyl monomer used here, styrene, acrylonitrile and the like are preferable. Furthermore, in the present invention, a copolymerizable crosslinkable monomer is used. The crosslinking monomer to be used is not particularly limited, but preferably ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate. , Divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, allyl cinnamate and the like, and these can be used alone or in combination of two or more.
[0028]
In addition, since the solvent resistance of the acrylic resin film containing this improves by using a copolymerizable crosslinkable monomer, it is preferable.
[0029]
The polymer (B-1) in the rubber-containing polymer (B) is necessary for enhancing the solvent resistance of the resulting film.
[0030]
In addition, in an elastic copolymer ((B-1) + (B-2)), a polymer (B-1) is 20-60 mass%, and a rubber polymer (B-2) is 80-40 mass%. It is preferable to contain in the range from a viewpoint of solvent resistance and film moldability.
[0031]
More preferably, the polymer (B-1) is present in an amount of 30% by mass or more in the elastic copolymer ((B-1) + (B-2)). When the rubber polymer (B-2) is present in the elastic copolymer ((B-1) + (B-2)), more preferably 50% by mass or more, the film moldability is improved.
[0032]
The glass transition temperature of the innermost layer polymer (B-1) needs to be 0 ° C. or higher and lower than 25 ° C. If it is less than 0 ° C., the solvent resistance of the film is inferior, and if it exceeds 25 ° C., the film formability is inferior, so that the industrial utility value is low. Considering both the solvent resistance and formability of the film, the preferred glass transition temperature of the innermost layer polymer (B-1) is in the range of 15 ° C. or higher and lower than 25 ° C.
[0033]
The rubber-containing polymer (B) has an outermost layer polymer (B-3) in the outer layer of the elastic copolymer ((B-1) + (B-2)), and the outermost layer polymer (B- 3) can be produced by graft polymerization of a monomer to an elastic copolymer ((B-1) + (B-2)). As a monomer used for graft polymerization, 50% by mass or more of alkyl methacrylate is used, and specific examples of alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, Examples include cyclohexyl methacrylate. Further, 50% by mass or less of a copolymerizable vinyl monomer is used, and these are not particularly limited. Specifically, alkyl acrylates such as methyl acrylate, butyl acrylate, and cyclohexyl acrylate are used. Examples include esters and styrene. The content of the outermost layer polymer (B-3) in the rubber-containing polymer (B) is 10 to 400 masses with respect to 100 mass parts of the elastic copolymer ((B-1) + (B-2)). Parts, preferably 20 to 200 parts by weight. When the content of the outermost layer polymer (B-3) is 10 parts by mass or more with respect to 100 parts by mass of the elastic copolymer ((B-1) + (B-2)), the elastic copolymer is aggregated. This is preferable because it is difficult to occur and the transparency becomes good.
[0034]
The rubber-containing polymer (B) used in the present invention must have a mass average particle diameter in the range of 0.2 to 0.4 μm. When the mass average particle diameter is less than 0.2 μm, the mechanical properties of the film when in contact with the solvent are deteriorated, and film-forming defects such as film breakage occur when an acrylic resin film is produced. On the other hand, if the mass average particle diameter exceeds 0.4 μm, the resulting film has poor transparency.
[0035]
Considering the solvent resistance, transparency and film-forming property of the film, the preferred mass average particle diameter of the rubber-containing polymer is 0.25 to 0.35 μm.
[0036]
The rubber-containing polymer (C) has a structure of one layer or two or more layers whose main component is an alkyl acrylate ester that is an inner layer. Both The polymer (C-1) is grafted with a hard polymer (C-2) having a structure of one layer or two or more layers in which the outer layer is a methacrylic acid alkyl ester as a main constituent of the polymer. It is a rubber-containing polymer having a multilayer structure of more than one layer and having a mass average particle diameter in the range of less than 0.2 μm.
[0037]
In obtaining the elastic copolymer (C-1), known alkyl ester of acrylic acid is used, among which butyl acrylate, acrylic acid-2-ethylhexyl and the like are preferable.
[0038]
The alkyl acrylate is used in the range of 35 to 100% by mass. Use of 35% by mass or more improves the film-forming property and solvent resistance of the film. A more preferable use range is 50% by mass or more.
[0039]
Also ,Both In obtaining the polymer (C-1), other vinyl monomers that can be copolymerized in a range of 65% by mass or less can be copolymerized. As the vinyl monomer used here, methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate and cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable, and these can be used alone or in combination of two or more. .
[0040]
Furthermore, a crosslinkable monomer is used. The crosslinkable monomer to be used is not particularly limited, but preferably ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl. Examples include isocyanurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, and allyl cinnamate, and these can be used alone or in combination.
[0041]
The crosslinkable monomer is used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the monomer mixture. It is preferable to use 0.3 mass part or more from the point of the solvent resistance of the acrylic resin film containing this. The use of 10 parts by mass or more is not particularly problematic, but the use amount of 10 parts by mass or less is preferable because the effect on the addition amount is small.
[0042]
Both The polymer (C-1) can have a structure of one layer or two or more layers. When the structure has two or more layers ,Both The content of the alkyl acrylate ester as a whole of the polymer (C-1) may be 35% by mass or more.
[0043]
In the case of a hard core structure, the content of the alkyl acrylate ester in the first layer can be 35% by mass or less. For example, a multilayer polymer having a hard core structure with a particle size of 0.2 μm or less as disclosed in JP-A-7-149994, although it is not described for use as a substitute for coating, can be used.
[0044]
As an outer layer ,Both As a constituent component of the hard polymer (C-2) grafted to the polymer (C-1), 50% by mass or more of alkyl methacrylate is used. Specifically, methyl methacrylate, ethyl methacrylate, methacryl Examples include butyl acid, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like. Further, at least one of the other copolymerizable vinyl monomers is used in an amount of 50% by mass or less, and is not particularly limited. Specifically, alkyl acrylates such as methyl acrylate, butyl acrylate, and cyclohexyl acrylate, Examples thereof include styrene and acrylonitrile, and these can be used alone or in combination of two or more.
[0045]
The content of the grafted hard polymer (C-2) is ,Both It is 10-400 mass parts with respect to 100 mass parts of polymers (C-1), Preferably it is 20-200 mass parts, and can prepare it by carrying out graft polymerization at least 1 step | paragraph or more.
[0046]
Grafted hard polymer (C-2) Both When it is less than 10 parts by mass relative to 100 parts by mass of the polymer (C-1) ,Both Transparency may deteriorate due to polymer aggregation.
[0047]
The mass average particle diameter of the rubber-containing polymer (C) used in the present invention must be less than 0.2 μm. Preferably it is 0.05-0.18 micrometer. The rubber-containing polymer (C) can be obtained by ordinary emulsion polymerization. When the mass average particle diameter is less than 0.2 μm, preferably 0.18 μm or less, both transparency and solvent resistance are improved. It is preferable that it is a mass mean particle diameter of 0.05 micrometer or more from a film forming viewpoint of the acrylic resin film containing this.
[0048]
The rubber-containing polymers (B) and (C) of the present invention can be obtained by known emulsion polymerization. The polymerization temperature varies depending on the kind and amount of the polymerization initiator used, but is preferably 40 to 120 ° C, more preferably 60 to 95 ° C.
[0049]
As the polymerization initiator, a known one can be used, and the addition method can be a method of adding to one or both of the aqueous phase and the monomer phase. As a particularly preferred example of the initiator, a peroxide, an azo initiator, or a redox initiator combined with an oxidizing agent / reducing agent is used. Among these, a redox initiator is more preferable, and a sulfoxylate initiator combined with ferrous sulfate / ethylenediaminetetraacetic acid disodium salt / longalite / hydroperoxide is particularly preferable.
[0050]
As the emulsifier, an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used, and an anionic surfactant is particularly preferable. Examples of anionic surfactants include rosin acid soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroylsarcosate, alkenyl succinate dipotassium salt, sulfate ester such as sodium lauryl sulfate, etc. Examples thereof include salts, sulfonic acid salts such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, and phosphoric acid ester salts such as sodium polyoxyethylene alkylphenyl ether phosphate.
[0051]
The rubber-containing polymer can be recovered from the polymer latex by treating the polymer latex obtained by the emulsion polymerization method by a known method such as an acid coagulation method, a salt coagulation method, a freeze coagulation method, or a spray drying method. As the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. As the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium chloride are used. Organic salts such as calcium acetate and magnesium acetate can be used. A powdered or granular polymer can be obtained by further washing, dehydrating and drying the coagulated and recovered polymer.
[0052]
The rubber-containing polymer (B) and the rubber-containing polymer (C) are prepared as a powdery or granular polymer by the above-mentioned method, respectively, and a rubber-containing polymer produced by an emulsion polymerization method. After mixing the polymer latex of (B) and the rubber-containing polymer (C), the mixture of the rubber-containing polymer (B) and the rubber-containing polymer (C) is powdered or granulated from the mixed latex by the above method. There is a method to collect as.
[0053]
The acrylic resin film of the present invention is an acrylic resin film containing the above-mentioned thermoplastic polymer (A), rubber-containing polymer (B) and rubber-containing polymer (C) as essential components. When the thermoplastic polymer (A) is not included and only the rubber-containing polymer (B) and the rubber-containing polymer (C) are essential components, the film-forming property is greatly reduced, and the film thickness is uniform. The film cannot be manufactured. In addition, when only the thermoplastic polymer (A) and the rubber-containing polymer (C) are included as essential components without including the rubber-containing polymer (B), the transparency of the film is good and the film is in contact with alcohols. Although there is little change in appearance such as discoloration, the deterioration of the mechanical properties of the film after contact with the solvent is large, and the acrylic resin film having such a large change in physical properties has a low industrial utility value because its use is limited. In addition, when only the thermoplastic polymer (A) and the rubber-containing polymer (B) are included as essential components without including the rubber-containing polymer (C), the transparency of the film, particularly when the thickness is less than 75 μm. The haze value of the film is large, and appearance changes such as whitening occur when it comes in contact with alcohols. Thus, the acrylic resin film having such a large change in appearance has a low industrial utility value because of limited applications. That is, an acrylic resin film having excellent transparency and a change in appearance upon contact with alcohols and a change in physical properties after contact with a solvent are thermoplastic polymer (A), rubber-containing polymer (B), and rubber-containing This can be achieved by using the polymer (C) as an essential component.
[0054]
In addition, as a similar technique of the present invention, an impact-resistant methacrylic resin containing two kinds of rubber components having different average particle diameters in specific ratios as disclosed in JP-A-62-285942 and JP-A-62-275147, etc. A composition is disclosed. However, the publication does not describe any specific method for improving the solvent resistance of the acrylic resin film, the use as an acrylic resin film, and the acrylic resin composition produced by the method of the examples. The acrylic resin film produced by using this material has a high haze value and whitening occurs when it comes into contact with alcohols. An acrylic resin film having excellent transparency and solvent resistance can never be obtained by the technique described in the publication. There is nothing. That is, an acrylic resin film excellent in transparency and solvent resistance is achieved for the first time by the present invention.
[0055]
The contents of the thermoplastic polymer (A), rubber-containing polymer (B) and rubber-containing polymer (C) constituting the acrylic resin film of the present invention are not particularly limited. The total of the rubber-containing polymer (B) and the rubber-containing polymer (C) is 5 to 100% by mass in the total of the thermoplastic polymer (A), the rubber-containing polymer (B), and the rubber-containing polymer (C). It is preferable that it is 40 mass%. When the total of the rubber-containing polymer (B) and the rubber-containing polymer (C) is less than 5% by mass, the film forming property of the acrylic resin film containing the polymer tends to be lowered, and the film is produced in a wound state. Tend to be difficult. On the other hand, in the range where the total of the rubber-containing polymer (B) and the rubber-containing polymer (C) exceeds 40% by mass, the mechanical properties after contact with the solvent of the acrylic resin film containing this tend to be lowered. Show. Considering both the film forming property of the acrylic resin film and the mechanical properties after contact with the solvent, the more preferable total content of the rubber-containing polymer (B) and the rubber-containing polymer (C) is a thermoplastic polymer. It is 10-35 mass% in a total of 100 mass% of (A), a rubber-containing polymer (B), and a rubber-containing polymer (C), More preferably, it is 20-33 mass%.
[0056]
Moreover, the mass ratio (B / C) of the rubber-containing polymer (B) and the rubber-containing polymer (C) constituting the acrylic resin film of the present invention is not particularly limited, but preferably 10/90. ~ 40/60. The mass ratio (B / C) is less than 10/90, that is, the content of the rubber-containing polymer (B) in the total content of 100% by mass of the rubber-containing polymer (B) and the rubber-containing polymer (C) is 10 When it is less than mass%, the mechanical properties of the acrylic resin film containing it tend to be deteriorated after contact with the solvent, while the mass ratio (B / C) exceeds 40/60, that is, rubber. When the content of the rubber-containing polymer (B) in the total content of 100% by mass of the containing polymer (B) and the rubber-containing polymer (C) exceeds 40% by mass, the transparency of the film is reduced. , It tends to easily change appearance such as whitening when contacted with alcohols. In consideration of all of the mechanical properties of the acrylic resin film after contact with the solvent, the decrease in transparency of the film and the appearance change such as whitening when contacted with alcohols, the more preferable range of the mass ratio (B / C) is It is 10 / 90-30 / 70, More preferably, it is 15 / 85-28 / 72.
[0057]
In addition to the contents of the thermoplastic polymer (A), rubber-containing polymer (B) and rubber-containing polymer (C) constituting the acrylic resin film, the elastic copolymer in the rubber-containing polymer (B) (B-1) and rubber-containing polymer (C) Both The total content of the polymer (C-1) is important for the film-forming properties of the acrylic resin film and the mechanical properties after contact with the solvent, and the preferred elastic co-polymer in the rubber-containing polymer (B) In coalescence (B-1) and rubber-containing polymer (C) Both The total content of the polymer (C-1) is 4 to 30% by mass in a total of 100% by mass of the thermoplastic polymer (A), the rubber-containing polymer (B), and the rubber-containing polymer (C). When the content is less than 4% by mass, the film-forming property of the acrylic resin film containing the same tends to be lowered. When the content exceeds 30% by mass, the mechanical properties after contact with the solvent of the acrylic resin film containing the same are exhibited. Shows a tendency to decrease. Considering both the film-forming property of the acrylic resin film and the mechanical properties after contact with the solvent, a more preferable elastic copolymer (B-1) Together with The total content of the polymer (C-1) is 10 to 25% by mass, more preferably 15 to 20% by mass.
[0058]
The acrylic resin film of this invention can contain the thermoplastic polymer (D) shown below as needed.
[0059]
Thermoplastic polymer (D)
It consists of 50 to 100% by mass of methyl methacrylate units and 0 to 50% by mass of at least one unit of other vinyl monomers copolymerizable therewith. The reduced viscosity of the polymer (0.1 g of polymer) A thermoplastic polymer that is dissolved in 100 mL of chloroform and measured at 25 ° C.) exceeding 0.2 L / g.
[0060]
By using the thermoplastic polymer (D), the film-forming property is improved, so that the effect is exhibited particularly when a high level of thickness accuracy and film-forming speed are required.
[0061]
When the reduced viscosity of the thermoplastic polymer (D) is in a range exceeding 0.2 L / g, a film with good thickness accuracy is obtained. The reduced viscosity of the thermoplastic polymer (D) used is usually more than 0.2 L / g and 2 L / g or less, preferably 1.2 L / g or less.
[0062]
In the thermoplastic polymer (D) used in the present invention, examples of vinyl monomers copolymerizable with methyl methacrylate include alkyl acrylate esters, alkyl methacrylate esters, aromatic vinyl compounds, vinyl cyanide compounds, and the like. Can be used. The polymerization is preferably carried out by an emulsion polymerization method, and it is produced by separating and collecting a polymer latex produced by a known emulsion polymerization method using various coagulants or separating and collecting a solid content by spray drying.
[0063]
In this invention, content of the thermoplastic polymer (D) used as needed is 0.1-10 mass parts with respect to (A) + (B) + (C) = 100 mass parts. If the amount is less than 0.1 parts by mass, the effect of improving the film-forming property due to the use of the thermoplastic polymer (D) is hardly exhibited. On the other hand, if the amount exceeds 10 parts by mass, the viscosity of the resin composition increases, It shows a tendency for transparency to decrease slightly.
[0064]
The acrylic resin film of the present invention may be a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact aid, a foaming agent, a filler, an antibacterial agent, an antifungal agent, if necessary. A foaming agent, a release agent, an antistatic agent, a colorant, a matting agent, an ultraviolet absorber, and the like can be included. Particularly in terms 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, particularly preferably 400 or more. If an ultraviolet absorber having a molecular weight of less than 300 is used, it may volatilize during vacuum molding or pressure molding in an injection mold, and mold contamination may occur. The type of the UV absorber is not particularly limited, but a benzotriazole type having a molecular weight of 400 or more or a triazine type having a molecular weight of 400 or more can be particularly preferably used. Specific examples of the former include Cinnabin 234 from Ciba Geigy, Specific examples of Adeka Stab LA-31 from the company, and Tinuvin 1577 from Ciba Geigy are listed as specific examples of the latter.
[0065]
As a method for adding the above compounding agent, a thermoplastic polymer (A), a rubber-containing polymer (B), a rubber-containing polymer (C) and a necessary material are used in a film-forming machine for forming the acrylic resin film of the present invention. A method of supplying together with a thermoplastic polymer (D) used according to the conditions, and a thermoplastic polymer (A), a rubber-containing polymer (B), a rubber-containing polymer (C), and a thermoplastic polymer used as necessary There is a method of kneading and mixing the mixture obtained by adding the compounding agent to (D) with various kneaders. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.
[0066]
The heat distortion temperature (measurement based on ASTM D648) of the acrylic resin film of the present invention is preferably 80 ° C. or higher. When the thermal deformation temperature is 80 ° C. or higher, surface roughness after heating of the laminate having an acrylic resin film on the surface is less likely to occur, and the solvent resistance tends to be improved. Further, when the heat distortion temperature is 80 ° C. or higher, for example, a treatment liquid for forming a photocatalyst layer for the purpose of preventing contamination on the acrylic resin film surface of the laminate having an acrylic resin film on the surface, a surface hardening liquid or an antistatic, Acrylic resin film surface with application and drying of various treatment liquids in this way can suppress warping, curvature, etc. due to shrinkage of the film in the drying treatment after applying the treatment liquid for preventing condensation etc. In applications that require modification, excellent process passability can be achieved, and the industrial utility value is high.
[0067]
The heat distortion temperature of the acrylic resin film of the present invention varies depending on the amount of the rubber-containing polymer (B) and the rubber-containing polymer (C) used, but the heat of the thermoplastic polymer (A) mainly constituting the film. Determined by deformation temperature. The heat distortion temperature of the thermoplastic polymer (A) can be adjusted by adjusting the monomer composition of the thermoplastic polymer (A) by a known method. Although it depends on various conditions, for example, when methyl methacrylate is used as a copolymerization component, when the thermal deformation temperature of the acrylic resin film is 80 ° C. or higher, the content of methyl methacrylate in the thermoplastic polymer (A) When the heat distortion temperature is 95 ° C. or higher, the methyl methacrylate content in the thermoplastic polymer (A) can be adjusted to 95 mass% or higher. When the heat distortion temperature is 100 ° C. or higher, it is necessary to copolymerize maleimides such as maleic anhydride and phenylmaleimide in the thermoplastic polymer (A). Of course, even when the heat distortion temperature is 80 ° C. or higher and 100 ° C. or higher, it is possible to copolymerize maleimides such as maleic anhydride and phenylmaleimide to reduce the methyl methacrylate content.
[0068]
Examples of the method for producing the acrylic resin film used in the present invention include known methods such as a melt casting method, a melt extrusion method such as a T-die method and an inflation method, and a calendar method. The die method is preferred.
[0069]
In the case of producing an acrylic resin film by the T-die method, a thermoplastic polymer (A), a rubber-containing polymer (B), a rubber-containing polymer (C), and a thermoplastic polymer (D used as necessary) ), A method of directly using a mixture obtained by metering various compounding agents, and a thermoplastic polymer (A), a rubber-containing polymer (B), a rubber-containing polymer (C), and a thermoplastic polymer used as necessary. (D) There is a method of using a pellet-shaped resin composition produced by melt-kneading a mixture of compounding agents in various kneaders such as a single screw extruder and a twin screw extruder as a raw material for film formation. .
[0070]
Although the thickness of the acrylic resin film of this invention is not specifically limited, Preferably it is 300 micrometers or less. When it is 300 μm or less, the rigidity and the secondary workability are facilitated because the rigidity becomes appropriate. Further, the film forming property is stable and the film can be easily manufactured. More preferably, they are 15 micrometers-200 micrometers, More preferably, they are 40 micrometers-200 micrometers.
[0071]
The acrylic resin film of this invention can manufacture the laminated body which has an acrylic resin film on the surface by laminating | stacking on the surface of base materials, such as various resin molded products, woodwork products, and metal molded products.
[0072]
In addition, in order to provide the design property to various base materials, the acrylic resin film of the present invention can be used after printing by an appropriate printing method as necessary. In this case, it is preferable to use an acrylic resin film that has been subjected to one-side printing treatment, and at the time of molding, it is preferable from the viewpoint of protecting the printing surface and imparting a high-class feeling to arrange the printing surface on the adhesive surface with the base resin. . Further, when the color tone of the base material is utilized and used as an alternative to transparent coating, it can be used as it is transparent. In particular, the acrylic resin film is superior in terms of transparency, depth and luxury in comparison with the polyvinyl chloride film and the polyester film for applications in which the color tone of the base material is utilized.
[0073]
Further, a matte treatment such as embossing on the film or a coloring treatment can be used as necessary.
[0074]
In applications where the acrylic resin film of the present invention is used as a paint substitute, painting requires a dozen or more coats to produce a sufficiently thick coating, which is costly and extremely productive. On the other hand, in the case of the acrylic resin film laminated molded product according to the present invention, since the acrylic resin film itself becomes a coating film, a very thick coating film can be easily formed, which is industrially advantageous. is there.
[0075]
The resin used as the base material for the acrylic laminated molded product used in the present invention must be capable of being melt-bonded to the acrylic resin film. ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride Resins, acrylic resins, polyester resins, or resins containing these as a main component can be mentioned. From the viewpoint of adhesiveness, ABS resins, AS resins, polycarbonate resins, vinyl chloride resins, or resins containing these resins as main components are preferable. More preferably, an ABS resin, a polycarbonate resin, or a resin containing these as a main component can be used. However, it is possible to adhere an acrylic resin film and a base material at the time of molding by using an adhesive layer even with a base material resin such as polyolefin resin that is not thermally fused.
[0076]
As a method for producing a laminate having the acrylic resin film of the present invention on the surface, when forming into a two-dimensional laminate, a known method such as thermal lamination may be used for a base material that can be heat-sealed. it can. Moreover, it is possible to bond together the base material which is not heat-sealed through an adhesive agent.
[0077]
On the other hand, when molding into a three-dimensional laminate, an insert molding method in which an acrylic resin film that has been processed in advance is inserted into an injection mold, an in-mold molding method in which injection molding is performed after vacuum molding in the mold, etc. Any known molding method can be used. These are particularly preferable as a molding method for producing a laminate from the viewpoint of productivity.
[0078]
In the in-mold molding method, after the acrylic resin film is heated, 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 can be molded and injection molded in one step. The heating temperature is preferably equal to or higher than the temperature at which the acrylic resin film softens. This depends on the thermal properties of the film or the shape of the molded product, but is usually 70 ° C. or higher. On the other hand, if the temperature is too high, the surface appearance deteriorates and the releasability deteriorates. Although this also depends on the thermal properties of the film or the shape of the molded product, it is usually preferably 170 ° C. or lower.
[0079]
Thus, when a three-dimensional shape is imparted to a film by vacuum forming, whitening of the mold corner and followability to the corner are important, and the characteristics of the acrylic resin film for paint replacement of the present invention can be utilized to the maximum. It is a processing method. The acrylic resin film has a high degree of elongation at high temperatures and is very advantageous.
[0080]
In the in-mold molding method, after giving a three-dimensional shape by vacuum molding in this way, an acrylic laminated molded product having an acrylic resin film layer on the surface layer is obtained by melting and integrating the acrylic resin film and the base resin by injection molding. be able to.
[0081]
The acrylic resin film of this invention or the laminated body which has an acrylic resin film on the surface can perform the surface treatment for various functions provision to the acrylic resin film surface as needed. Surface treatments for imparting functions include printing processes such as silk printing and inkjet printing, metal deposition for imparting metal tone or antireflection, sputtering, wet plating treatment, surface hardening treatment for improving surface hardness, and contamination prevention. Water repellent treatment or photocatalyst layer formation treatment, antistatic treatment for the purpose of dust adhesion prevention or electromagnetic wave cutting, etc., among these, taking advantage of the excellent solvent resistance characteristic of the acrylic resin film of the present invention The surface treatment includes a step of applying a surface treatment agent containing an organic solvent to the acrylic resin film and a surface treatment including a drying step, and further comprising a step of applying a surface treatment agent containing alcohols to the acrylic resin film and a drying step. Even if the surface treatment is performed, the intended surface treatment can be performed without discoloration such as whitening.
[0082]
The industrial application field of the laminate having the surface of the acrylic resin film of the present invention is not particularly limited, but for example, automobile interior parts such as console boxes and shift lever boxes, and vehicle exterior parts such as cowlings of motorcycles. It can also be used for materials that have been conventionally painted, such as home appliances, furniture, and building materials. In the above fields, various solvents that adhere to and contact the surface of the acrylic resin film on the outermost surface under the usage environment of the member, such as alcohols such as ethanol and isopropanol contained in fragrance liquids, hair styling, etc. Excellent solvent resistance is exhibited, and discoloration such as whitening can be suppressed by contact with the solvent.
[0083]
Further, as another industrial application field of the laminate having the surface of the acrylic resin film of the present invention, there is a high-intensity reflective material used for a road sign, a display board, or a safety device for the purpose of visibility. The types of high-brightness reflectors include capsule-type reflectors in which aluminum-deposited glass beads are embedded in the substrate, and prism-type reflectors that use a prism-processed resin sheet as a reflector. In addition, the acrylic resin film of the present invention can be used as a protective film that is used by being laminated on the surface of a reflective material. The high-brightness reflector having the acrylic resin film of the present invention on its surface not only has good solvent resistance against the solvent that comes into contact during use, but also, for example, a photocatalyst aimed at preventing contamination on the acrylic resin film surface of the reflector Discoloration such as whitening, cracking, and deformation such as bending do not occur even by applying a treatment liquid containing aromatic hydrocarbons and / or alcohols used in the treatment for forming a layer, and drying performed after application. Therefore, industrial use value is very high.
[0084]
【Example】
The following examples illustrate the invention.
[0085]
In the reference examples, examples and comparative examples, “part” represents “part by mass” and “%” represents “% by mass”. Abbreviations in the reference examples are as follows.
[0086]
Methyl methacrylate MMA
Methyl acrylate MA
Butyl acrylate BA
Styrene St
Allyl methacrylate AMA
1.3-Butylene glycol dimethacrylate 1.3BD
t-Butyl hydroperoxide tBH
t-Hexyl hydroperoxide tHH
n-octyl mercaptan nOM
Further, evaluation of properties of thermoplastic polymer (A), rubber-containing polymer (B) and rubber-containing polymer (C) prepared in Reference Examples and Examples, acrylic resin films prepared in Reference Examples, and laminates including the same Various physical properties of the body were measured by the following test methods.
[0087]
1) Reduced viscosity of thermoplastic polymer (A) and thermoplastic polymer (D)
0.1 g of the polymer was dissolved in 100 mL of chloroform and measured at 25 ° C.
[0088]
2) Mass average particle diameter of rubber-containing polymer (B) and rubber-containing polymer (C)
Measure the polymer latex of the rubber-containing polymer (B) or rubber-containing polymer (C) obtained by emulsion polymerization using a dynamic light scattering method using a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd. Shimoto.
[0089]
3) Glass transition temperature of polymer (B-1)
Using a DSC (DSC200 manufactured by Seiko Denshi Kogyo Co., Ltd.), measurement was performed using the obtained rubber-containing polymer (B) powder to determine the glass transition temperature of the polymer (B-1) component. .
[0090]
4) Total light transmittance and haze value of the film
Evaluation was made according to JIS K6714.
[0091]
5) Surface gloss of film
The surface gloss of the film was measured at 60 ° using a gloss meter (GM-26D type, manufactured by Murakami Color Research Laboratory).
[0092]
6) Pencil hardness of the laminate
Evaluation was made according to JIS K5400.
[0093]
7) Film formability
A film having a thickness of 50 μm was formed by the T-die method, a film that could be formed without being cut for 5 hours or more, a film that was cut several times in 5 hours, and a film that was cut. Therefore, the sample that could not be obtained was marked as x.
[0094]
8) Thermal deformation temperature of the film composition
The film composition pellet was formed into a heat distortion temperature measurement specimen based on ASTM D648 by injection molding, annealed at 80 ° C. for 24 hours, and then measured according to ASTM D648 at low load (0.45 MPa).
[0095]
9) Alcohol resistance test of laminate
Three sheets of 10 mm × 10 mm flannel cloth in which ethanol (reagent grade 1) was swollen were placed on the acrylic resin film surface side of the laminate, and a 30 cc glass bottle was placed over the flannel cloth and allowed to stand at room temperature for 3 hours. . Next, the glass bottle and flannel cloth were removed, and the appearance of the laminate acrylic resin film surface after leaving the laminate for 1 hour at room temperature was visually evaluated, and the alcohol resistance was determined by the following index.
[0096]
○: No change, Δ: Slight whitening is observed, ×: Whitening is observed
10) Solvent contact test of acrylic resin film
Ten acrylic resin films having a width of 15 mm, a length of 120 mm, and a thickness of 50 μm were prepared and fixed on a jig so as to be vertically suspended, and a weight having a mass of 10 g was suspended at the lower end. Subsequently, toluene was apply | coated to the position of 50 mm from the lower end of an acrylic resin film, and the time until each film fracture | ruptured was measured. The mechanical properties of the acrylic resin film after contact with the solvent were determined from the average values of the time until breaking of 8 sheets excluding the minimum value and the maximum value of the time until breaking of 10 sheets by the following index.
[0097]
○: Time to average break> 60 seconds
Δ: 60 seconds ≧ time to average break ≧ 30 seconds
X: 30 seconds> time to average break
Reference Example 1 Production of rubber-containing polymer (B)
In a nitrogen atmosphere, 244 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, the temperature was raised to 80 ° C., (i) shown below was added, and the following raw materials (b) (polymer) were added while stirring. 1/15 of the mixture of (B-1)) was charged and held for 15 minutes. Thereafter, the remaining (b) was continuously added at an increase rate of 8% / hour of the monomer mixture with respect to water. Thereafter, the polymer (B-1) was polymerized by maintaining for 1 hour.
[0098]
Subsequently, 0.6 parts of sodium formaldehyde sulfoxylate was added to the latex, and the mixture was held for 15 minutes, and the following raw materials (c) (rubber polymer (B-2) were obtained while stirring at 80 ° C. in a nitrogen atmosphere. ) Was continuously added at an increase rate of the monomer mixture to water of 4% / hour. Thereafter, the rubber polymer (B-2) was polymerized by holding for 2 hours to obtain a polymer latex of an elastic polymer.
[0099]
Subsequent to the obtained elastic polymer latex, 0.4 part of sodium formaldehyde sulfoxylate was added, and then kept for 15 minutes, while stirring at 80 ° C. in a nitrogen atmosphere, The outer layer polymer (B-3)) was continuously added at an increase rate of 10% / hour of the monomer mixture with respect to water. Thereafter, the outermost layer polymer (B-3) was polymerized by maintaining for 1 hour to obtain a polymer latex of the rubber-containing polymer (B). The rubber-containing polymer (B) obtained had a mass average particle diameter of 0.28 μm.
[0100]
Coagulation, aggregation, and solidification reaction of polymer latex of rubber-containing polymer (B) using an aqueous solution of calcium acetate twice the amount of latex (concentration of 3 parts of calcium acetate to rubber-containing polymer (B)) After filtration, washing with water and drying, a rubber-containing polymer (B) was obtained.
[0101]
From the DSC measurement of the obtained rubber-containing polymer (B), the glass transition temperature of the polymer (B-1) component was 24 ° C.
[0102]
(I)
0.6 parts of sodium formaldehyde sulfoxylate
Ferrous sulfate 0.00012 parts
Ethylenediaminetetraacetic acid disodium 0.0003 parts
(B)
MMA 22.0 parts
15.0 parts of BA
St 3.0 parts
AMA 0.4 part
1.3BD 0.14 parts
tBH 0.18 parts
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
60% di (polyoxyethylene nonylphenyl ether) phosphoric acid
1.0 part of neutralized product of sodium hydroxide mixture
(C)
50.0 parts of BA
St 10.0 parts
AMA 0.4 part
1.3BD 0.14 parts
tHH 0.2 parts
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
60% di (polyoxyethylene nonylphenyl ether) phosphoric acid
1.0 part of neutralized product of sodium hydroxide mixture
(D)
MMA 57.0 parts
MA 3.0 parts
nOM 0.3 parts
tBH 0.06 parts
(Reference Example 2) Production of rubber-containing polymer (C)
(Ii ') shown below was charged into a reaction vessel, and the raw material (b') was continuously added at 80 ° C for 200 minutes under stirring in a nitrogen atmosphere, followed by further polymerization for 120 minutes, to obtain an elastic polymer ( C-1) polymer latex was obtained.
[0103]
Obtained Together To the polymer (C-1) latex, the following (c ′) is added, and the following raw materials (d ′) are continuously added over 100 minutes at 80 ° C. in a nitrogen atmosphere while stirring. Thereafter, polymerization was carried out by holding at 80 ° C. for 60 minutes to obtain a polymer latex of a rubber-containing polymer (C). The rubber-containing polymer (C) obtained had a mass average particle diameter of 0.12 μm.
[0104]
The rubber-containing polymer (C) latex is coagulated, agglomerated and solidified using an aqueous solution of calcium acetate twice the amount of latex (concentration at which the amount of calcium acetate to the rubber-containing polymer (C) is 3 parts). After filtration, washing with water and drying, a rubber-containing polymer (C) was obtained.
[0105]
(I')
310 parts deionized water
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
60% di (polyoxyethylene nonylphenyl ether) phosphoric acid
0.5 parts of partially neutralized sodium hydroxide mixture
Sodium carbonate 0.1 parts
Sodium formaldehyde sulfoxylate 0.5 parts
Ferrous sulfate 0.00024 parts
Ethylenediaminetetraacetic acid disodium 0.00072 parts
(Ro ')
81.0 parts of BA
St 19.0 parts
AMA 1.0 part
0.25 parts tBH
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
60% di (polyoxyethylene nonylphenyl ether) phosphoric acid
1.1 parts of partially neutralized mixture of sodium hydroxide
(Ha ')
10 parts of deionized water
Sodium formaldehyde sulfoxylate 0.15 parts
(D ')
MMA 57.0 parts
MA 3.0 parts
nOM 0.2 parts
tBH 0.1 part
(Reference Example 3) Production of thermoplastic polymer (D)
A reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and 1 part of an emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. Subsequently, 40 parts of MMA, 10 parts of BuA, and 0.005 part of NOM were charged and stirred at 65 ° C. for 3 hours under a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of MMA and 2 parts of BuA was added dropwise over 2 hours, and kept for 2 hours after completion of the addition to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, and the polymer was acid coagulated, then dehydrated, washed with water, and dried to recover the thermoplastic polymer (D) in powder form. The resulting thermoplastic polymer (D) had a reduced viscosity ηsp / c of 0.38 L / g.
[0106]
Examples 1 to 4 and Comparative Examples 1 to 5 Production of acrylic resin films (F-1 to 4 and G-1 to 5) and production of laminates having these on the surface
MMA / MA copolymer (MMA / MA = 99/1, reduced viscosity 0.06 L / g) which is a thermoplastic polymer (A), rubber-containing polymer (B) and rubber produced in Reference Examples 1 to 3 As a compounding agent, 0.4 part of “Adeka Stub P” manufactured by Asahi Denka Co., Ltd., Asahi Denka, Inc. After adding 0.1 part of “Adeka Stub AO-60” manufactured by Co., Ltd., 1.0 part of “Tinubin 1577” manufactured by Ciba Specialty Chemicals Co., Ltd. and 0.8 part of “Metabrene L1000” manufactured by Mitsubishi Rayon Co., Ltd. The mixture was mixed using a Henschel mixer, and the mixture was supplied to a degassing extruder (PCM-30 manufactured by Ikekai Tekko Co., Ltd.) heated to 230 ° C. and kneaded to obtain pellets.
[0107]
The results of the heat distortion temperature measured using the obtained pellets are shown in Table 1.
[0108]
The pellets produced by the above method were dried overnight at 80 ° C., and a cylinder temperature of 200 ° C. to 240 ° C. was measured using a 40 mmφ non-vented screw type extruder (L / D = 26) equipped with a 300 mm wide T die. A film having a thickness of 50 μm was formed at a die temperature of 250 ° C. and a cooling roll temperature of 70 ° C. The film forming property evaluation results are shown in Table 1.
[0109]
Table 1 shows the measurement results of the total light transmittance, haze, surface gloss, and solvent contact test of each acrylic resin film obtained.
[0110]
Next, the obtained acrylic resin film was subjected to gravure printing to produce a printed film having a wood grain pattern. Next, the printed film was heated at 140 ° C. for 1 minute, and then vacuum-formed with a mold having a vacuuming function. An acrylic resin in which ABS resin ("Diapet ABS3001" manufactured by Mitsubishi Rayon Co., Ltd.) is injection-molded on the printing surface and printed on the surface of the ABS resin molded product with the molded film placed in an injection mold. A laminate in which films were laminated was obtained.
[0111]
Table 1 shows the results of pencil hardness measurement and alcohol resistance test performed using the obtained laminate.
[0112]
[Table 1]

From the examples and comparative examples, the following became clear.
[0113]
1) The acrylic resin films (F-1 to 4) of Examples 1 to 4 all have good film-forming properties, transparency, surface gloss and good mechanical property retention after contact with a good solvent. Shows alcohol resistance. In particular, the balance between the retention of mechanical properties and the alcohol resistance after contact with the solvent of the acrylic resin films (F-1 and 2) of Examples 1 and 2 is at a high level not found in conventionally known acrylic resin films. In addition, the industrial use value of the acrylic resin film having excellent solvent resistance is high.
[0114]
2) All of the acrylic resin films of Comparative Examples 4 and 5 have poor film-forming properties, and a film having a uniform thickness of 50 μm cannot be obtained. Evaluation of the film and a laminate using the film is difficult. It was impossible.
[0115]
3) The acrylic resin films (G-1 and 3) not containing the rubber-containing polymer (C) of Comparative Examples 1 and 3 are all film-forming properties, surface gloss, and mechanical property retention after contact with a solvent. Is good, but the alcohol resistance is poor, and when the laminate using this on the surface is contacted with alcohol, discoloration such as whitening occurs, and thus the acrylic resin film laminate in which the appearance change occurs, Since the use which can be used is limited, industrial utility value is low.
[0116]
In addition, the acrylic resin films (G-1 and 3) not containing the rubber-containing polymer (C) of Comparative Examples 1 and 3 both have a high haze value at 50 μm, and have a high level of design, especially the surface of the laminate. It cannot be used for applications that require deep transparency.
[0117]
4) The acrylic resin film (G-2) which does not contain the rubber-containing polymer (B) of Comparative Example 2 has good film-forming properties, transparency, surface gloss and alcohol resistance, but after contact with the solvent. Acrylic resin film with poor mechanical resistance due to a significant decrease in mechanical properties, for example, when it comes into contact with a processing solution containing a solvent such as printing or surface treatment, the strength of the film decreases and handling properties are impaired. Has a low industrial utility value because of limited uses.
[0118]
【The invention's effect】
The present invention is as described above, and has a particularly remarkable effect as described below, and its industrial utility value is extremely large.
[0119]
1) The acrylic resin film of the present invention is excellent in film forming properties, transparency, surface gloss, surface hardness, and solvent resistance.
[0120]
2) The balance between the retention of mechanical properties especially after contact with the solvent and the alcohol resistance of the laminate having the same on the surface is a very high level that cannot be obtained with conventionally known acrylic resin films. The utility value as an industrial material, especially as a film material for lamination, is extremely high.

Claims (7)

An acrylic resin film containing the following (A), (B) and (C).
Thermoplastic polymer (A)
It is composed of 50 to 100% by mass of methacrylic acid alkyl ester units, 0 to 50% by mass of acrylic acid alkyl ester units and 0 to 49% by mass of at least one unit of other vinyl monomers copolymerizable therewith. A thermoplastic polymer having a combined viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of 0.1 L / g or less.
Rubber-containing polymer (B)
A rubber-containing polymer (B) comprising an elastic polymer ((B-1) + (B-2)) comprising a polymer (B-1) and a rubber polymer (B-2), wherein the innermost layer is A polymer (B-1) having a glass transition temperature of 0 to 25 ° C. having a methacrylic acid alkyl ester or an acrylic acid alkyl ester as a main component, and an intermediate layer having a glass transition point having an acrylate alkyl ester as a main component The mass average particle diameter having a three-layer structure comprising a rubber polymer (B-2) having a temperature of less than 0 ° C. and an outermost layer polymer (B-3) having an outermost layer mainly composed of an alkyl methacrylate ester. A rubber-containing polymer in the range of 0.2 to 0.4 μm.
Rubber-containing polymer (C)
Co-polymers that have a one or more layers of structural Ru inner layer der in (C-1), one or more layers of the structure as a main constituent of the methacrylic acid alkyl ester is a layer polymer rigid polymer (C-2) is obtained by grafting with, a rubber-containing polymer with a weight average particle size having a multilayer structure of two or more layers is in the range of less than 0.2 [mu] m, the copolymer ( A rubber-containing polymer in which 35 to 100% by mass of an alkyl acrylate is used for obtaining C-1) . The acrylic resin film according to claim 1, further comprising the following thermoplastic polymer (D).
Thermoplastic polymer (D)
It consists of 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of at least one other vinyl monomer copolymerizable therewith, and the reduced viscosity of the polymer (0.1 g of polymer is dissolved in 100 mL of chloroform. , Measured at 25 ° C.) exceeding 0.2 L / g.  The acrylic resin film according to claim 1, wherein the total of the component (B) and the component (C) is 5 to 40% by mass with respect to the total of 100% by mass of the component (A), the component (B) and the component (C). The total of the elastic copolymer (B-1) and the copolymer (C-1) is 4 to 30% by mass with respect to the total of 100% by mass of the component (A), the component (B) and the component (C). The acrylic resin film according to claim 1.  The acrylic resin film according to claim 1, wherein the mass ratio (B / C) of the component (B) to the component (C) is from 10/90 to 40/60.  The acrylic resin film of Claim 1 whose heat-deformation temperature (measurement based on ASTM D648) is 80 degreeC or more.  The laminated body which has the acrylic resin film of Claim 1 on the surface.