JP3977658B2 - Acrylic resin film, method for producing the same, and laminated sheet on which the same is laminated - Google Patents

Description

【発明の効果】
以上説明したように、本発明によれば、本来のアクリル樹脂フィルムの特長を損なうことなく、熱ラミネート時の加熱ロールとの剥離性にも優れたアクリル樹脂フィルム、その製造方法およびそれを積層した積層シートが提供できる。[0001]
BACKGROUND 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 in which the film is laminated.
[0002]
[Prior art]
Acrylic resin is excellent in transparency, has a beautiful appearance and weather resistance, and is easy to mold, so it is widely used in applications such as electrical parts, vehicle parts, optical parts, ornaments, signs, etc. . However, as the use of acrylic resins expands, further performance improvement according to the use is being studied. Among these, in recent years, acrylic resin films for the purpose of imparting surface functions to various resin molded products have been used in various industrial fields. These acrylic resin films are laminated and used 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, These substrates are applied to impart weather resistance and scratch resistance. As a method of laminating an acrylic resin film to a base sheet, etc., 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 a film and bonded to a base sheet, etc. The most industrially widely used is a thermal laminate in which an acrylic resin film is preheated with a heating roll, laminated on a base sheet, and bonded by sandwiching a laminate between a plurality of rolls. However, in this heat laminating method, there is a problem that the acrylic resin film is hardly peeled off from the preheating roll by long-term continuous operation, and is wound around the heating roll. Furthermore, in the thermal laminating method, the acrylic resin side becomes difficult to peel off from the roll by long-term continuous operation in the process of sandwiching the laminate composed of the base sheet and the acrylic resin film with a plurality of rolls, There was a problem. In order to prevent wrapping around these rolls, there are methods such as lowering the temperature of the pre-heating roll and lowering the pressure of the sandwiching roll. When the embossing roll is used to form the uneven surface, the embossing followability is lowered, and there is a problem that the laminate cannot be manufactured stably.
[0003]
On the other hand, since the dry lamination method uses an organic solvent and an adhesive, there are problems such as an environmental problem and a manufacturing cost that is higher than that of the heat lamination method.
[0004]
[Problems to be solved by the invention]
The purpose of the present invention is to maintain the features such as good moldability, beautiful appearance, high transparency, excellent weather resistance, etc. inherent to acrylic resins, and with a heating roll for heat laminating with a base sheet. An object of the present invention is to provide an acrylic resin film excellent in peelability and to provide a laminated sheet that is industrially rich in production.
[0005]
[Means for Solving the Problems]
The gist of the present invention is (meth) acrylic acid hydroxyalkyl ester, carbon having a surfactant of 0.05 to 10 parts by mass and an alkyl group having 1 to 8 carbon atoms with respect to 100 parts by mass of acrylic resin (I). 0.1 to 30 parts by mass of a linear polymer (II) having a hydroxyl group comprising an alkyl ester having an alkyl group of 1 to 4 and an alkyl ester of acrylic acid and another vinyl monomer capable of copolymerization The blended film cut to φ10 mm is sandwiched between metal plates with a surface roughness of # 250, pressed at 170 ° C for 8 minutes with a load of 7 kg, and then peeled off when the metal plates are peeled off in the vertical direction. The acrylic resin film has a strength of 30 kgf or less and a surface gloss of 80 to 120%.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described.
[0007]
The acrylic resin film of the present invention has a strength of 30 kgf or less when a metal plate having a surface roughness of # 250 is sandwiched between a metal plate having a surface roughness of # 250, subjected to a load of 7 kg and pressed at 170 ° C. for 8 minutes and then peeled off. There must be. When the strength when peeling the metal plate exceeds 30 kgf, when the acrylic resin film is thermally laminated with the base sheet, the peelability from the sandwiching roll becomes poor, and the winding around the roll occurs and the laminated sheet is stable. Can not be manufactured.
[0008]
On the other hand, the surface gloss of the acrylic resin film of the present invention needs to be 80 to 120%. When the surface gloss of the acrylic resin film is less than 80%, the transparency inherent in the acrylic resin film is impaired, and when it exceeds 120%, the peelability from the heating roll deteriorates, so that the winding around the preheating roll is not possible. It 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.
[0009]
The acrylic resin (composition) constituting the acrylic resin film of the present invention is not particularly limited, but film compositions made of known acrylic resins, for example, Japanese Examined Patent Publication Nos. 62-19309 and 63- It is preferable to use an acrylic resin composition disclosed in Japanese Patent Application Laid-Open No. 20459, Japanese Patent Application Laid-Open No. 63-77963, Japanese Patent Application Laid-Open No. 8-323934, and the like.
[0010]
Preferable examples of the acrylic resin (I) used in the production of the acrylic resin film of the present invention include a multilayer structure heavy comprising an alkyl acrylate, an alkyl methacrylate, and a graft-crossing agent known as a known technique as constituent components of the polymer. The acrylic resin film which is a coalescence and uses this as a film raw material has excellent weather resistance, transparency and stress whitening resistance.
[0011]
More specific examples of the preferred multilayer structure polymer include 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 at least as a constituent component of the polymer. An innermost layer polymer (A) layer, a cross-linked elastic polymer (B) having at least an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and a graft crossing agent as constituents of the polymer, and having 1 to 4 carbon atoms The outermost layer polymer (C) having at least an alkyl methacrylate having an alkyl group as a constituent component of the polymer as a basic structure, and further between the crosslinked elastic polymer (B) layer and the outermost layer polymer (C) layer In addition, alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and alkyl group having an alkyl group having 1 to 4 carbon atoms. At least one intermediate layer (D) comprising at least one acrylate and a graft crossing agent, and the amount of the alkyl acrylate component monotonously decreasing from the crosslinked elastic polymer (B) layer toward the outermost polymer (C) layer. It has a multilayer structure polymer.
[0012]
The innermost layer polymer (A) constituting the preferred multilayer structure polymer is an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (A1), and if necessary. The other component (A2) having a copolymerizable double bond, a polyfunctional monomer (A3) used as necessary, and a graft crossing agent (A4) are used as constituents. It is a coalescence and constitutes the basic structure of at least the innermost layer of the multilayer structure.
[0013]
Of the component (A1) constituting the innermost layer polymer (A), the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms may be either 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 can 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. In addition, among the components (A1), the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms may be either linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like. These can be used alone or in admixture of two or more.
[0014]
The alkyl (meth) acrylate (A1) is preferably used within a 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). The alkyl (meth) acrylate of the type used in the innermost layer polymer (A) is most preferably used afterwards in all multi-stage layers. However, in each of all the multistage layers, two or more kinds of alkyl (meth) acrylates may be mixed, or another kind of acrylate may be used. “(Meth) acrylate” means acrylate and / or methacrylate.
[0015]
The other monomer (A2) having a copolymerizable double bond constituting the innermost layer polymer (A) may be used as necessary. Specific examples thereof include acrylate monomers such as higher alkyl acrylate, lower alkoxy acrylate and cyanoethyl acrylate having an alkyl group having 9 or more carbon atoms, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylo A nitrile etc. are mentioned. The monomer (A2) is preferably used within a range of 0 to 20 parts by mass with respect to 100 parts by mass in total of the components (A1) to (A3).
[0016]
What is necessary is just to use the polyfunctional monomer (A3) which comprises an innermost layer polymer (A) as needed. As specific examples thereof, alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate are preferably used. Further, polyvinyl benzene such as divinyl benzene and trivinyl benzene can also be used. Further, even when the polyfunctional monomer (A3) does not act at all, as long as the graft crossing agent is present, a considerably stable multilayer structure polymer is obtained. For example, when the hot strength or the like is strictly required, it may be arbitrarily used depending on the purpose of addition. It is preferable to use a polyfunctional monomer (A3) within the range of 0-10 mass parts with respect to 100 mass parts in total of components (A1)-(A3).
[0017]
Examples of the graft crossing agent (A4) constituting the innermost layer polymer (A) include allyl, methallyl or crotyl ester of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Particularly preferred are acrylic esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid. Among these, allyl methacrylate has an excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. In the graft crossing agent (A4), the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group or crotyl group, and chemically bonds. During this time, a substantial portion of the allyl, methallyl or crotyl group works effectively during the polymerization of the next layer polymer to provide a graft bond between adjacent two layers.
[0018]
The amount of the grafting agent (A4) used is important, and is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the total amount of the components (A1) to (A3). . The lower limit of these ranges is significant in terms of the effective amount of graft bonds. In addition, the upper limit is that the amount of reaction with the crosslinked elastic polymer (B) polymerized and formed in the second stage is moderately suppressed, and the elasticity of the two-layer crosslinked rubber elastic body having a two-layer elastic body structure is prevented. it makes sense.
[0019]
The content of the innermost layer polymer (A) in the preferred multilayer structure polymer is preferably 5 to 35% by mass, more preferably 5 to 15% by mass. Further, the content is preferably smaller than the content of the crosslinked elastic polymer (B).
[0020]
The cross-linked elastic polymer (B) constituting the preferred multilayer structure polymer is a main component that gives rubber elasticity to the multilayer structure polymer, and an alkyl acrylate (B1) having an alkyl group having 1 to 8 carbon atoms and necessary As a constituent, another monomer (B2) having a copolymerizable double bond used according to the above, a polyfunctional monomer (B3) used as necessary, and a graft crossing agent (B4) It is a crosslinked elastic polymer.
[0021]
Preferable specific examples of the components (B1) to (B4) are the same as those described for the components (A1) to (A4) of the innermost layer polymer (A). 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. As for the usage-amount of a component (B3), 0-10 mass parts is preferable. The amount of component (B4) used is preferably 0.1 to 5 parts by mass. The range of these usage-amounts is based on 100 mass parts of components (B1)-(B3) in total.
[0022]
The Tg of the crosslinked elastic polymer (B) alone is preferably 0 ° C. or lower, and more preferably −30 ° C. or lower. When this Tg is 0 ° C. or lower, there is a tendency to exhibit excellent elasticity. The content of the cross-linked elastic polymer (B) in the multilayer structure polymer (E) is preferably 10 to 45% by mass, and preferably more than the content of the innermost layer polymer (A).
[0023]
The outermost layer polymer (C) constituting the preferred multilayer structure polymer is a component involved in the moldability and mechanical properties of the multilayer structure polymer, and is an alkyl methacrylate (C1 having an alkyl group having 1 to 4 carbon atoms). ) And another monomer (C2) having a copolymerizable double bond used as necessary, which constitutes a constituent component, and constitutes at least the outermost basic structure of the multilayer structure.
[0024]
Preferred specific examples of the components (C1) and (C2) are the same as those described for the components (A1) and (A2) of the innermost layer polymer (A). As for the usage-amount of a component (C1), 51-100 mass parts is preferable. The amount of component (C2) used is preferably 0 to 49 parts by mass. The range of these amounts used is based on a total of 100 parts by mass of components (C1) and (C2).
[0025]
The Tg of the outermost layer polymer (C) alone is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher. 10-80 mass% is preferable and, as for content of the outermost layer polymer (C) in a multilayer structure polymer, 40-60 mass% is more preferable.
[0026]
A preferred multilayer structure polymer has the innermost layer polymer (A), the cross-linked 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 polymer (C) layer.
[0027]
This intermediate layer (D) can be copolymerized with an alkyl acrylate (D1) having an alkyl group having 1 to 8 carbon atoms, an alkyl methacrylate (D2) having an alkyl group having 1 to 4 carbon atoms, if necessary. Other monomer (D3) having a double bond, a polyfunctional monomer (D4) used as necessary, and a graft crossing agent (D5) as constituents of the polymer, and alkyl acrylate In this layer, the component amount monotonously decreases from the crosslinked elastic polymer (B) layer toward the outermost polymer (C) layer.
[0028]
Here, monotonically decreasing means that the intermediate layer (D) has a composition at one point between the cross-linked elastic polymer (B) and the outermost layer polymer (C). It means that the composition gradually (continuously) approaches the coalescence (C) and that the composition approaches in steps, and in particular, the one having an intermediate composition at one point is good in terms of productivity.
[0029]
Preferable specific examples of the components (D1) to (D5) are the same as those described for the components (A1) to (A4) of the innermost layer polymer (A). In particular, the graft crossing agent (D5) used for the intermediate layer (D) is a component necessary for tightly bonding the polymer layers and obtaining excellent properties.
[0030]
As for the usage-amount of a component (D1), 10-90 mass parts is preferable. As for the usage-amount of a component (D2), 10-90 mass parts is preferable. As for the usage-amount of a component (D3), 0-20 mass parts is preferable. As for the usage-amount of a component (D4), 0-10 mass parts is preferable. The amount of component (D5) used is preferably 0.1 to 5 parts by mass. The range of these usage-amounts is based on 100 mass parts of components (D1)-(D4) in total.
[0031]
It is preferable that content of the intermediate | middle layer (D) in a preferable multilayer structure polymer is 5-35 mass%. If content is 5 mass%-35 mass%, the acrylic resin film which has the outstanding softness | flexibility and workability can be obtained.
[0032]
The average particle diameter of the multilayer structure polymer of a preferred example used for the production of the acrylic resin film of the present invention is in the range of 0.08 to 0.2 μm in consideration of the mechanical properties and transparency of the film mainly composed thereof. Is preferred.
[0033]
In addition, the multilayer structure polymer includes 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 cross-linking agent to give the innermost layer polymer (A) layer. An emulsion prepared by mixing at least a monomer mixture containing 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 polymer ( The monomer or monomer mixture that gives C) can also be supplied to the reactor in order, and polymerization can be carried out, in terms of reducing the huge polymer particles distributed in the range of 1 to 200 μm present in the acrylic resin latex. preferable.
[0034]
The weight ratio of the acrylic resin latex monomer mixture to water is preferably 10 parts to 500 parts of water with respect to 100 parts of the monomer mixture, more preferably 100 parts of water to 100 parts of the monomer mixture. The range is 300 parts.
[0035]
As the surfactant used in preparing the emulsion, an anionic, cationic, and 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, dipotassium alkenyl succinate, and sulfate esters such as sodium lauryl sulfate. 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.
[0036]
In addition, as a method for preparing an emulsion, a method of charging a surfactant after charging a monomer mixture in water, a method of charging a monomer mixture after charging a surfactant into water, a monomer Examples thereof include a method in which water is added after a surfactant is charged into the mixture. Among these, the method of charging the surfactant after adding the monomer mixture into water and the method of charging the monomer mixture after charging the surfactant into water are the methods for obtaining the multilayer structure polymer of the present invention. preferable.
[0037]
Further, as a mixing apparatus for preparing an emulsion prepared by mixing a monomer mixture that gives the innermost layer polymer (A) layer with water and a surfactant, a stirrer, a homogenizer, a homogenizer equipped with a stirring blade are used. Various forced emulsifiers such as mixers, membrane emulsifiers and the like can be mentioned.
[0038]
In addition, as the emulsion to be prepared, any dispersion structure of W / O type and O / W type can be used, but in particular, O / W type in which oil droplets of a monomer mixture are dispersed in water, The diameter of the oil droplets in the dispersed phase is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 15 μm or less. When it exceeds 100 μm, the number of huge polymer particles distributed in the range of 1 to 200 μm contained in the obtained acrylic resin latex tends to increase.
[0039]
The innermost layer polymer (A) layer, the cross-linked elastic polymer (B) layer, the intermediate layer (D) layer, and the outermost layer polymer (C) constituting the preferred multilayer structure polymer used for the production of the acrylic resin film of the present invention. ) Known polymerization initiators can be used for forming the layer, and the addition method can be either the aqueous phase or the monomer phase, or a method of adding to both. 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.
[0040]
In particular, the above-mentioned innermost layer polymer (A) layer, cross-linked elastic polymer (B) layer, intermediate layer (D), and outermost layer polymer (C) and the monomer or monomer mixture are sequentially fed into the reactor. In the method of polymerizing by supplying to an aqueous solution, the temperature of an aqueous solution containing ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite is raised to the polymerization temperature, and then the innermost layer polymer (A) is fed to the reactor for polymerization. Then, a monomer mixture which gives a cross-linked elastic polymer (B) layer, an intermediate layer (D) and an outermost layer polymer (C) containing a polymerization initiator such as a peroxide is sequentially supplied to the reactor for polymerization. Is the most preferable method for obtaining the multilayer structure polymer used in the present invention.
[0041]
The multilayer structure polymer preferable as a raw material of 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-described method. The method of recovering the multilayer structure polymer from the polymer latex is not particularly limited, and examples thereof include salting out or acid precipitation coagulation, spray drying, freeze drying, and the like, and the powder is recovered in powder form.
[0042]
As the surfactant to be added when the acrylic resin film of the present invention is molded, a known one can be used, and a surfactant containing an alkyl sulfonate is preferable, and it contains dioctyl sodium sulfosuccinate. A surfactant is more preferable from the viewpoint of roll peelability of the acrylic resin film.
[0043]
The surfactant added when molding the acrylic resin film of the present invention may be added when pelletizing, may be added when molding the film, but is added when molding the film. More preferably. Addition at the time of film forming is advantageous in terms of peelability from a heating roll during lamination and thermal stability of the surfactant. When added when pelletizing the surfactant, it receives a lot of thermal history, which may accelerate the deterioration of the acrylic resin by heat and cause fish eyes and the like, and the effect of roll peelability is reduced. Sometimes. It is preferable that the compounding quantity of surfactant at the time of film forming is the range of 0.05-10 mass parts with respect to 100 mass parts of acrylic resins (I). When the compounding amount of the surfactant is less than 0.05 parts by mass, the peelability from the laminate roll is poor, and when it exceeds 10 parts by mass, the appearance of the film is deteriorated. A more preferable range of use is 0.1 to 5 parts by mass for peelability from the laminate roll and good appearance.
[0044]
The linear polymer (II) contained in the acrylic resin film of the present invention is not particularly limited, but a (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 1 carbon atom. Examples include linear polymers composed of methacrylic acid alkyl esters having 4 to 4 alkyl groups, acrylic acid alkyl esters, and other copolymerizable vinyl monomers, such as acrylic acid hydroxyalkyl esters and / or methacrylic acid. 1 to 80% by weight of hydroxyalkyl ester, 10 to 99% by weight of alkyl methacrylate, 0 to 79% by weight of acrylic acid alkyl ester, and 0 to 50% by weight of at least one other copolymerizable vinyl monomer. Intrinsic viscosity is in the range of 0.3 L / g or less, and it contains no components insoluble in chloroform. Those having a hydroxyl group.
[0045]
Examples of the hydroxyalkyl ester of acrylic acid and / or hydroxyalkyl methacrylate used for the linear polymer (II) having a hydroxyl group include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid 2, 3 -Dihydroxypropyl, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and the like are included. Among these, 2-hydroxyethyl methacrylate is particularly preferable.
[0046]
Content in the linear polymer (II) which has a hydroxyl group of acrylic acid hydroxyalkyl ester or / and methacrylic acid hydroxyalkyl ester is the range of 1-80 mass%. If it is less than 1% by mass, the effect of peelability from the laminate roll is insufficient. On the other hand, when it exceeds 80% by mass, the dispersibility of the particles is deteriorated, and when the film is formed, undispersed particles are present, and the appearance may be deteriorated. A preferable use range is 5 to 50% by mass for peelability from the laminate roll and good appearance. More preferably, it is the range of 10-40 mass%.
[0047]
As the alkyl methacrylate, lower alkyl methacrylates 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 in the range of 30 to 90% by mass.
[0048]
The acrylic acid alkyl ester is preferably contained in a range of up to 79% by mass, and specifically, a lower acrylic acid alkyl ester such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like is preferable. The alkyl acrylate is preferably contained in the range of 0.5 to 40% by mass. More preferably, it is 5-25 mass%.
[0049]
It is preferable that the linear polymer (II) having a hydroxyl group does not contain a component insoluble in chloroform. Components insoluble in chloroform remain as unmelted nuclei when made into an acrylic resin film, causing poor appearance. Specifically, the intrinsic viscosity, Mw / Mn (Mw is a weight average molecular weight, Mn is a number average molecular weight) which is a molecular weight distribution, cullet generated during polymerization, and the like are important.
[0050]
The intrinsic viscosity of the linear polymer (II) having a hydroxyl group is preferably adjusted to a range of 0.3 L / g or less, and the linear polymer (II) having an unmelted hydroxyl group in the acrylic resin film is selected. It is necessary to reduce.
[0051]
The smaller the intrinsic viscosity, the better the dispersibility of the linear polymer (II) having a hydroxyl group in the acrylic resin film, so the number of the linear polymer (II) having a hydroxyl group that causes poor appearance is reduced. . It is preferable to adjust to the range of 0.12 L / g or less, and it is still more preferable to adjust to the adjustment of 0.06 L / g or less. For the adjustment, a polymerization regulator such as mercaptan is used. As the mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and the like are used.
[0052]
Although the manufacturing method of the linear polymer (II) which has a hydroxyl group used for manufacture of the acrylic resin film of this invention is not specifically limited, The method by suspension polymerization or emulsion polymerization is preferable.
[0053]
As the initiator for suspension polymerization, those used for usual suspension polymerization are used, and examples thereof include organic peroxides and azo compounds.
[0054]
As the suspension stabilizer, known ones commonly used are used, and examples thereof include organic colloidal polymer materials, inorganic colloidal polymer materials, inorganic fine particles, and combinations of these with surfactants. 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. In addition, it is preferable that an inorganic dispersant can be removed by the treatment after polymerization because it does not adversely affect the appearance.
[0055]
Suspension polymerization is usually carried out by suspending the monomers together with a polymerization initiator in the presence of a suspension stabilizer. In addition, it is also possible to carry out by using a polymer soluble in the monomer dissolved in the monomer.
[0056]
Post-treatment after suspension polymerization is important, and it is preferable to remove cullet, which is a component insoluble in chloroform generated during polymerization, which causes poor film appearance, by sieving. For example, those not containing a cullet of 300 μm or more, preferably those not containing a cullet of 100 μm or more are used. Although it is more preferable not to contain cullet of 100 μm or less from the viewpoint of the appearance of the film, in this case, normal beads are also removed by sieving, resulting in a decrease in yield.
[0057]
In order to efficiently remove cullet by sieving without reducing the product yield, the average particle diameter of the linear polymer having a hydroxyl group is preferably 300 μm or less. More preferably, it is 200 micrometers or less.
[0058]
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). When the blending amount is 0.1 parts by mass or less, the peelability from a sufficient laminate roll is slightly lowered, and when the blending amount is more than 30 parts by mass, the workability during film forming tends to be slightly lowered. In order to obtain good peelability, 0.5 part by mass or more is more preferable.
[0059]
When the linear polymer (II) having a hydroxyl group is used, the peelability from the preheating roll can be improved without deteriorating physical properties such as film elongation. Therefore, the film can be used satisfactorily without incurring film breakage or the like even in in-mold forming such as vacuum forming of the film in advance.
[0060]
In the production of the acrylic resin film of the present invention, powder can be used as a raw material, and since the pellet production process can be omitted, the acrylic resin film can be produced at low cost.
[0061]
In this case, the powder preferably has an average particle size of 500 μm or more. When the average particle size of the powder is less than 500 μm, the supply to the film forming machine tends to be unstable, and film thickness unevenness tends to occur. On the other hand, the upper limit of the average particle diameter of the powder is not particularly limited as long as it is a size that allows film forming. However, it is difficult to produce a powder having a large particle size. Moreover, although it is possible to obtain large particles by sieving, there are problems such as high processing costs.
[0062]
This average particle diameter is a value calculated by sieving for 30 minutes with an M-2 type micro-type electromagnetic vibration sieve manufactured by Tsutsui Rika Instruments Co., Ltd.
[0063]
The thermoplastic polymer (III) used in the production of the acrylic resin film of the present invention is a reduction obtained by polymerizing methyl methacrylate and another monomer having a copolymerizable double bond used as necessary. It is a thermoplastic polymer having a viscosity (0.1 g of a polymer dissolved in 100 ml of chloroform and measured at 25 ° C.) of 0.2 to 2 l / g.
[0064]
This thermoplastic polymer (III) is a component (processing aid) showing an important role for 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 the film moldability of the resulting acrylic resin film. On the other hand, when it exceeds 2 l / g, the film moldability tends to decrease. The particularly preferred reduced viscosity of the thermoplastic polymer (III) is in the range of 0.2 to 1.2 l / g.
[0065]
In the thermoplastic polymer (III), the content of methyl methacrylate is preferably 50% by mass or more. This content is based on 100% by mass in total of methyl methacrylate and other monomers having a double bond copolymerizable therewith.
[0066]
In the polymerization of methyl methacrylate in order to obtain the thermoplastic polymer (III), another monomer having a double bond can be copolymerized. When other monomers are used, the content is preferably 50% by mass or less. This content is based on 100% by mass in total of methyl methacrylate and other monomers having a double bond copolymerizable therewith.
[0067]
In the thermoplastic polymer (III) used for the production of the acrylic resin film of the present invention, aromatic vinyl compounds, vinylcyan compounds, and the like can be used as vinyl monomers copolymerizable with methyl methacrylate. Examples of the aromatic vinyl compound include styrene, α-substituted styrene, nucleus-substituted styrene and derivatives thereof, for example, α-methylstyrene, chlorostyrene, vinyltoluene and the like.
[0068]
Furthermore, examples of the vinylcyan compound include acrylonitrile and methacrylonitrile.
[0069]
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. The method for recovering the emulsion latex of the thermoplastic polymer (III) is not particularly limited. Specific examples include salting out or acid precipitation solidification, spray drying, freeze drying, and the like, and the powder can be recovered in a powder form.
[0070]
As for the compounding quantity of thermoplastic polymer (III) used by manufacture of the acrylic resin film of this invention, 0.1-20 mass parts is preferable with respect to 100 mass parts of acrylic resins (I). When the thermoplastic polymer (III) is less than 0.1 parts by mass, the effect of suppressing the generation of fish eyes tends to be insufficient, and when it exceeds 20 parts by mass, the melt viscosity increases and the film formability decreases. There is a tendency.
[0071]
The method for supplying the thermoplastic polymer (III) used in the production of the acrylic resin film of the present invention to a single-screw extruder with a film forming machine is not particularly limited, and the thermoplastic polymer (III) And the acrylic resin (I), which is a powder having an average particle diameter of 500 μm or more mainly composed of an acrylic resin, may be quantitatively supplied to the single-screw extruder attached to the film forming machine.
[0072]
As a specific example of supplying the thermoplastic polymer (III) to the single-screw extruder attached to the film forming machine, the thermoplastic polymer (III) produced by emulsion polymerization or suspension polymerization is mainly composed of an acrylic resin. A method of measuring, mixing and feeding together with acrylic resin (I) which is a powder having an average particle diameter of 500 μm or more, and an acrylic resin which is a powder having an average particle diameter of 500 μm or more from a master batch pellet containing thermoplastic polymer (III) A method of measuring, mixing and supplying together with (I) is mentioned. Among these, in particular, the method using master batch pellets containing the thermoplastic polymer (III) as a raw material is more preferable because it can suppress the occurrence of optical distortion of the resulting acrylic resin film. The optical distortion referred to here means streak-like or annual ring-like fluctuations generated on the film surface and inside the film. The optical distortion in the acrylic resin film is, for example, pasted on the window glass as described in “Technology and application of functional film” [CMC Co., Ltd., issued July 30, 1982] page 128. When used as a window glass to be used together, it appears as distortion of the image of the outside world seen through the glass, and is important from the viewpoint of external visibility. In general, it is difficult to evaluate the optical distortion of a film numerically as described in the above-mentioned document, but it can be evaluated based on the magnitude of distortion of an external image obtained by passing the film through a specific angle.
[0073]
Master batch pellets can be produced by kneading and extruding thermoplastic polymer (III) and acrylic resin (I). For kneading and extrusion, a single screw extruder or a twin screw extruder can be usually used. It is preferable that content of the thermoplastic polymer (III) in a masterbatch pellet is 0.1-30 mass parts with respect to 100 mass parts of acrylic resins (I). When the thermoplastic polymer (III) is less than 0.1 parts by mass, the thermoplastic polymer (III) in the acrylic resin film obtained by a method using a master batch pellet containing the thermoplastic polymer (III) as a raw material Since the amount becomes insufficient, the film formability tends to decrease. When the amount exceeds 30 parts by mass, the melt viscosity increases, so the kneadability of the masterbatch pellet decreases, and the acrylic resin produced using this as a raw material The appearance of the film tends to deteriorate. In addition, although the acrylic resin used for masterbatch pellet manufacture is not specifically limited, Use of the above-mentioned acrylic resin used when manufacturing an acrylic resin film is preferable. Further, in the master batch pellet, a compounding agent for imparting various properties to the acrylic resin film obtained by the method of the present invention, such as a stabilizer, an ultraviolet absorber, a processing aid, a plasticizer, an impact resistance aid, A foaming agent, a filler, a colorant, a matting agent, a release agent, an antibacterial agent, and the like can be blended.
[0074]
Moreover, the compounding quantity in the case of using a master batch pellet is not particularly limited, but is preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic resin (I). When the pellet obtained by kneading and extruding the thermoplastic polymer (III) and the acrylic resin (I) which is a powder having an average particle diameter of 500 μm or more is less than 1 part by mass, the acrylic resin film tends to be optically distorted. . More preferably, it is 5 mass parts or more, More preferably, it is 7 mass parts or more.
[0075]
Moreover, when there are many compounding quantities of a masterbatch pellet, since it has the fault that the cost and energy concerning shaping become large, it is desirable to reduce as much as possible.
[0076]
When film forming is performed using acrylic resin (I), which is a powder having an average particle diameter of 500 μm or more, it is desirable to dry the powder to a moisture content of 0.3% or less with a dryer. The acrylic resin (I) has a hygroscopic property, and if the moisture content exceeds 0.3%, defects such as foaming, cracking 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 reaching a constant weight and reducing the mass.
[0077]
The drying method is not particularly limited, and examples thereof include dehumidified air drying, hot air drying, vacuum drying, and electromagnetic wave drying. Among the drying methods described above, drying methods other than dehumidifying air drying usually take a batch drying method using a plurality of dryers, and thus it is difficult to dry continuously. On the other hand, dehumidified air drying is advantageous for continuous production because it can be continuously dried, and is preferable in terms of equipment space, equipment cost, and the like. Moreover, it is preferable to install a rotary valve and a bridge breaker in the discharge part of a dryer.
[0078]
By the drying process as described above, the moisture content of the acrylic resin (I), which is a powder having an acrylic resin as a main component and an average particle diameter of 500 μm or more, is reduced to 0.3% or less, and this is attached to the film forming machine. It is fed into a single screw extruder, kneaded and extruded to form a film.
[0079]
Although the thickness of the acrylic resin film of this invention is not specifically limited, Preferably it is 10-500 micrometers. When the thickness is 10 to 500 μm, an appropriate rigidity is obtained, so that laminating properties, secondary workability, and the like are facilitated. 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.
[0080]
Further, the method for forming the acrylic resin film of the present invention is not particularly limited, and examples thereof include known solution casting methods, melt extrusion methods such as a T-die method, and an inflation method. In this respect, the T-die method is the most preferable method.
[0081]
The heat distortion temperature (measured based on 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, surface roughness after heating of the laminate having the film on the surface is less likely to occur. In addition, when the thermal deformation temperature is 80 ° C. or higher, for example, when a laminated body whose surface is roughened by embossing or the like is heat-processed, it is possible to suppress a deterioration in design due to glossy return of the embossed surface, Industrial value is high when an acrylic resin film is used for such a use.
[0082]
In addition, the acrylic resin film of the present invention may contain general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact aids, foaming agents, fillers, antibacterial agents, antibacterial agents, if necessary. Molding agents, foaming agents, mold release agents, antistatic agents, coloring agents, matting agents, ultraviolet absorbers 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. When an ultraviolet absorber having a molecular weight of less than 300 is used, it may volatilize on a transfer roll or the like when producing a film, thereby causing roll contamination. 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 Adeka Stab LA-31 from the company, and Tinuvin 1577 from Ciba Geigy are listed as specific examples of the latter.
[0083]
As a method for adding the above compounding agent, a method of supplying the film to a film forming machine for forming a film using an acrylic resin together with the acrylic resin and a mixture in which the compounding agent is previously added to the acrylic resin are kneaded and mixed in various kneaders. There is a way to do it. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.
[0084]
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.
[0085]
In addition, the acrylic resin film of the present invention can be used after printing by an appropriate printing method as necessary in order to impart design properties to various substrates. In this case, it is preferable to use an acrylic resin film that has been subjected to one-side printing treatment, and it is preferable from the viewpoint of protecting the printed surface and imparting a high-quality feeling to the printed surface to be bonded to 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 of the present invention is superior in terms of transparency, depth and luxury in comparison with the polyvinyl chloride film and the polyester film for applications that make use of the color tone of the substrate.
[0086]
Further, a matte treatment such as embossing on the film or a coloring treatment can be used as necessary.
[0087]
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 a resin mainly composed of these. A resin, an AS resin, a polycarbonate resin, a vinyl chloride resin, or a resin sheet mainly composed of these resins is preferable. However, it is possible to adhere the acrylic resin film of the present invention and the base material by using an adhesive layer even with a base resin that is not thermally fused, such as a polyolefin resin sheet.
[0088]
The acrylic resin film or the acrylic resin film laminated sheet of the present invention can be used by being bonded to various resin molded products, woodwork products and metal molded products. As a method of bonding the laminated sheet to the base material, a method using an adhesive, a method using adhesive processing, a heat laminating method, a laminated sheet or a member obtained by preforming a laminated sheet in advance at the time of injection molding is inserted into a mold. And an in-mold molding method.
[0089]
Among the resin molded products, examples of the thermoplastic resin molded product that can be melt-bonded to the acrylic resin film of the present invention include the resins described above.
[0090]
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.
[0091]
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. In the in-mold molding method, after the 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, when the temperature is too high, the surface appearance is deteriorated or the releasability is deteriorated. 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.
[0092]
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.
[0093]
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 forming treatment, antistatic treatment for preventing dust adhesion or electromagnetic wave cutting, antireflection layer formation, antiglare treatment and the like.
[0094]
As industrial uses of the acrylic resin film or laminated sheet of the present invention, various industries such as window frames, door materials, decorative steel plates, wall materials, furniture, construction sheets such as wallpaper, home appliance housing skin materials, vehicle interior skin materials, etc. It is a product and can be used as a covering material for the purpose of imparting design properties to the substrate and protecting the substrate.
[0095]
【Example】
The following examples illustrate the invention.
[0096]
In the examples and comparative examples, “part” represents “part by mass” and “%” represents “% by mass”. Abbreviations in the reference examples are as follows.
[0097]
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): sodium hydroxide partial neutralized product of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid [trade name Phosphanol LO529, Toho Chemical Co., Ltd.]
Preparation Example 1: Production of multilayer 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 0.20 part of sodium formaldehyde sulfoxylate and 0.0001 part of ferrous sulfate were added to 5 parts of ion-exchanged water. The mixture prepared by adding 0.0003 parts of EDTA was added all at once. Next, with stirring under nitrogen, a monomer mixture consisting of 0.3 part of MMA, 4.5 parts of BA, 0.2 part of BD, 0.05 part of AMA, 0.025 part of CHP and 1.3 parts of emulsifier (1) After dropping the mixture into the polymerization vessel over 8 minutes, the reaction was continued for 15 minutes to complete the polymerization of the innermost layer polymer (A-4). Subsequently, a monomer mixture consisting of 1.5 parts of MMA, 22.5 parts of BA, 1.0 part of BD, and 0.25 part of AMA was added over 90 minutes together with 0.016 part of CHP, and then the reaction was continued for 60 minutes to obtain crosslinking elasticity. A two-layer crosslinked rubber elastic body containing the polymer (B-4) was obtained.
[0098]
Subsequently, after a mixture of 6 parts of MMA, 4 parts of BA, 0.075 part of AMA, and 0.0125 part of CHP was dropped into the polymerization vessel over 45 minutes, the reaction was continued for 60 minutes to form an intermediate layer (D-4). It was.
[0099]
Next, a monomer mixture consisting of 55.2 parts of MMA, 4.8 parts of BA, 0.19 part of n-OM and 0.08 part of t-BH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes. The outermost layer polymer (C-4) was formed to obtain a polymer latex of the multilayer structure polymer (I-1).
[0100]
Preparation Example 2: Production of multilayer structure polymer (I-2) latex
After charging 8.5 parts of ion-exchanged water into a container equipped with a stirrer, a monomer mixture consisting of 0.3 part of MMA, 4.5 parts of BA, 0.2 part of BD, 0.05 part of AMA, and 0.025 part of CHP is added. And mixed with stirring. Next, 1.3 parts of the emulsifier (1) was added to the vessel while stirring, and stirring was continued again for 20 minutes to prepare an emulsion (N-1). The average particle size of the dispersed phase in the obtained emulsion was 10 μm.
[0101]
Next, 186.5 parts of ion exchange water is put into a polymerization vessel equipped with a cooler, the temperature is raised to 70 ° C., and 0.20 part of sodium formaldehyde sulfoxylate is added to 5 parts of ion exchange water. A mixture prepared by adding 0.0001 part of iron and 0.0003 part of EDTA was added all at once. Next, the emulsion (N-1) was dropped into the polymerization vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to complete the polymerization of the innermost layer polymer (A-1). Subsequently, a monomer mixture consisting of 1.5 parts of MMA, 22.5 parts of BA, 1.0 part of BD, and 0.25 part of AMA was added over 90 minutes together with 0.016 part of CHP, and then the reaction was continued for 60 minutes to obtain crosslinking elasticity. A two-layer crosslinked rubber elastic body containing the polymer (B-1) was obtained.
[0102]
Subsequently, after a mixture of 6 parts of MMA, 4 parts of BA, 0.075 part of AMA, and 0.0125 part of CHP was dropped into the polymerization vessel over 45 minutes, the reaction was continued for 60 minutes to form an intermediate layer (D-1). It was.
[0103]
Next, a monomer mixture consisting of 55.2 parts of MMA, 4.8 parts of BA, 0.19 part of n-OM and 0.08 part of t-BH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes. The outermost layer polymer (C-1) was formed to obtain a polymer latex of the multilayer structure polymer (I-2).
[0104]
Preparation Example 3: Production of linear polymer (II) having a 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.
[0105]
MA 10 parts by mass
60 parts by mass of MMA
30 parts by mass of HEMA
n-OM 0.08 parts by mass
0.5 parts by mass of LPO
MMA / methacrylate
/ Copolymer of ethyl methacrylate sulfonate 0.05 parts by mass
Sodium sulfate 0.5 parts by mass
250 parts by mass of ion exchange water
After sufficiently replacing the inside of the container with nitrogen gas, the mixture was heated to 75 ° C. while stirring, and polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C. and held for another 45 minutes to complete the polymerization, followed by sieving under the condition of 150 mesh openings, and the passed beads were dehydrated and dried to form a linear chain having a hydroxyl group. Polymer (II) was obtained.
[0106]
The polymer was measured by the following method to find that its intrinsic viscosity was 0.11 L / g, Mw / Mn was 1.9, and the average particle size was 70 μm.
[0107]
(Intrinsic viscosity of a linear polymer having a hydroxyl group)
Intrinsic viscosity and reduced viscosity were measured at 25 ° C. using chloroform as a solvent using an AVL-2C automatic viscometer manufactured by Sun Electronics. In the measurement of reduced viscosity, 0.1 g of a sample dissolved in 100 ml of chloroform was used.
[0108]
(Measurement of dispersion ratio (Mw / Mn) of linear polymer having hydroxyl group)
Using Shimazu LC-6A system (manufactured by Shimadzu Corp.) and connecting three KF-802.5, KF-804 and KF-805 (manufactured by Showa Denko) as GPC columns, using THF as the solvent Measured in terms of polystyrene.
[0109]
(Average particle diameter of linear polymer having a hydroxyl group)
The average particle diameter of the obtained polymer having a hydroxyl group was measured using a laser diffraction / scattering particle size distribution analyzer LA-910 manufactured by HORIBA.
[0110]
In addition, about the heating roll peelability, it carried out by the method shown below.
[0111]
<Method for testing peelability of single mirror roll>
The acrylic resin film was rotated at a speed of 5 rpm while being brought into contact with a 40φ mirror roll, and the acrylic resin film was taken up in the vertical direction from the mirror roll surface. The heating temperature of the mirror roll at this time was 140 ° C., and the contact between the film and the mirror roll was set to be half of the circumference of the mirror roll.
[0112]
The film was taken out for 30 minutes under the above conditions. The case where the acrylic resin film was not taken on the roll was indicated as “◯”, and the case where the acrylic resin film was wound around the roll without peeling off from the roll was indicated as “x”.
[0113]
<Embossing roll peelability test method>
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. In addition, the heating temperature of the embossing roll at this time was 140 degreeC, and the pressure when pinching with each roll was 4.9 MPa.
[0114]
The film was taken out for 30 minutes under the above conditions. The case where the acrylic resin film was not taken on the roll was indicated as “◯”, and the case where the acrylic resin film was wound around the roll without peeling off from the roll was indicated as “x”.
[0115]
<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 then washed with water to obtain a multilayered polymer in a wet powder form.
[0116]
Subsequently, this powdery multilayer structure polymer was squeezed and dehydrated at a cylinder temperature of 190 to 210 ° C. using a 35 mmφ screw type twin screw extruder (L / D = 26) to obtain a granular powder having an average particle size of 650 μm. . 100 parts of the granular powder and 0.5 part of aerosol OT-B (trade name, component: sodium dioctyl succinate = 85%, sodium benzoate = 15%) manufactured by Mitsui Cytec Co., Ltd. as a surfactant 1 part of the linear polymer (II) having a hydroxyl group obtained in Example 3 as a thermoplastic polymer (III), Metablene P-530A (trade name, reduced viscosity: 0.375 l) manufactured by Mitsubishi Rayon Co., Ltd. / G) 1 part, 1.5 parts of Tinuvin P (trade name) manufactured by Ciba Geigy Co., Ltd. as an ultraviolet absorber, 0.1 part of Adeka Stub AO-50 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. 0.8 parts of METABRENE L-1000 (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used and mixed with an automatic weighing and mixing apparatus [manufactured by Tamaki Co., Ltd., auto blender].
[0117]
Next, the mixture was melt-kneaded and pelletized at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C. using a 40 mmφ screw type extruder (L / D = 26). The pellets were dried at 80 ° C. for a whole day and night, and formed into a 0.05 mm thick film using a T-die with a 115 mmφ extruder to obtain an acrylic resin film of the present invention.
[0118]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0119]
<Example 2>
Granular powder of a multilayer structure polymer having an average particle diameter of 650 μm was obtained in the same manner as in Example 1 except that the acrylic resin latex obtained in Preparation Example 2 was used. Furthermore, the acrylic resin film was obtained like Example 1 using granule powder.
[0120]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0121]
<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 Methbrene P-530A, 0.1 parts of ADK STAB AO-50 Part, 0.8 parts of methabrene L-1000, mixed by an automatic metering and mixing device, using a 40 mmφ twin screw extruder (L / D = 26) at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C. It was melt-kneaded and pelletized.
[0122]
100 parts of the pellets, 1.5 parts of Tinuvin P as an ultraviolet absorber and 0.5 parts of aerosol OT-B were blended and formed into a 0.05 mm thick film using a T die with a 115 mmφ extruder. An acrylic resin film of the invention was obtained.
[0123]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0124]
<Example 4>
An acrylic resin film was obtained in the same manner as in Example 1 except that 3 parts of aerosol OT-B was used.
[0125]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0126]
<Example 5>
100 parts of the granule 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, and 1 part of methabrene P-530A Parts, Tinuvin P 1.5 parts, Adeka Stub AO-50 0.1 parts, and Metabrene L-1000 0.8 parts were mixed with an automatic measuring and mixing device.
[0127]
This mixture was formed into a 0.05 mm-thick film using a T-die with a 115 mmφ extruder to obtain an acrylic resin film of the present invention.
[0128]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0129]
<Example 6>
100 parts of the granule powder produced in Example 1, 5 parts of the linear polymer (II) obtained in Preparation Example 3, 5 parts of Metabrene P-530A, 0.5 part of AO-50, Metabrene L -1000 was mixed with an automatic measuring and mixing device [4 parts and melt-kneaded using a 40 mmφ screw type extruder (L / D = 26) at a cylinder temperature of 200 to 260 ° C and a die temperature of 250 ° C to be pelletized. .
[0130]
20 parts of the pellets, 80 parts of the granulated powder produced in Example 1, 0.5 parts of aerosol OT-B and 1.5 parts of tinuvin P were blended and 0.05 mm using a T die with a 115 mmφ extruder. The acrylic resin film of the present invention was obtained by forming into a thick film.
[0131]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0132]
<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.
[0133]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0134]
<Comparative Example 1>
An acrylic resin film was obtained in the same manner as in Example 1 except that aerosol OT-B was not used.
[0135]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0136]
<Comparative example 2>
An acrylic resin film was obtained in the same manner as in Example 1 except that 0.05 part of Aerosol OT-B was used.
[0137]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0138]
<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 obtained acrylic resin film had many fish eyes and poor appearance.
[0139]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0140]
<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.
[0141]
Table 1 shows the surface gloss, peel strength, and roll peelability evaluation results of the film.
[0142]
[Table 1]

【The invention's effect】
As described above, according to the present invention, an acrylic resin film excellent in releasability from a heating roll at the time of thermal lamination, a method for producing the same, and a laminate thereof are laminated without impairing the characteristics of the original acrylic resin film. Laminated sheets can be provided.

Claims (2)

  (Meth) acrylic acid hydroxyalkyl ester or alkyl having 1 to 4 carbon atoms having a surfactant of 0.05 to 10 parts by mass and an alkyl group having 1 to 8 carbon atoms with respect to 100 parts by mass of acrylic resin (I) To φ10 mm, 0.1 to 30 parts by mass of a linear polymer (II) having a hydroxyl group composed of a methacrylic acid alkyl ester having a group, an acrylic acid alkyl ester and another copolymerizable vinyl monomer After the cut film is sandwiched between metal plates with a surface roughness of # 250 and pressed at 170 ° C. for 8 minutes with a load of 7 kg, the peel strength when peeling the metal plate vertically is 30 kgf or less. An acrylic resin film having a surface gloss of 80 to 120%.   An acrylic resin film laminate sheet obtained by laminating the acrylic resin film according to claim 1 on a thermoplastic resin film or sheet.