JP3523565B2 - Acrylic resin film for lamination and acrylic laminated molded product using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic laminated molded product obtained by laminating and bonding a specific acrylic resin film, and a laminated acrylic resin film used for producing such a molded product.

[0002]

2. Description of the Related Art As a method for decorating the surface of a plastic product, there are roughly classified a direct printing method and a transfer method. The direct printing method is a method of directly printing on a molded product, and there are a pad printing method, a curved surface silk printing method, an electrostatic printing method, etc.
It is not suitable for the production of molded products having complicated shapes, and it is difficult to impart a high degree of designability. The transfer method includes a thermal transfer method and a water transfer method, but there is a problem that the cost is relatively high.

As a method other than the above, there is an in-mold molding method as a method of imparting a design property to a molded product at low cost. This method is to insert a sheet or film of printed polyester resin, polycarbonate resin, acrylic resin, etc. into a three-dimensional shape by vacuum molding or the like in advance, or insert it into an injection molding die without molding. The resin to be the base material is injection-molded, and the resin sheet or film may be integrated with the base resin, or the printing may be transferred to the surface of the base resin.

Acrylic resin films suitable for in-mold molding are disclosed in, for example, JP-A-8-323934 and JP-A-11-147237.

[0005]

In recent years, molded articles having an acrylic resin film layer on the surface layer formed by such an in-mold molding method have been used for automobile interiors and the like. In JP-A-8-323934, an acrylic resin film having excellent surface hardness, heat resistance, and moldability is obtained by using a smaller amount of rubber having a specific particle diameter than in the past.

However, when a suction cup made of PVC or the like containing a plasticizer such as DOP is attached to a member having such films laminated, there is a problem that whitening occurs due to aging. For example, when the temperature of the center console panel, the window switch panel, etc. is easily exposed to direct sunlight and the temperature becomes high, or when the temperature in summer is high, this becomes a particular problem.

In Japanese Patent Laid-Open No. 11-147237, an acrylic resin film having an excellent surface hardness is obtained by using a rubber having a hard core structure, but details required for exhibiting an excellent plasticizer whitening resistance. There is no particular description about the rubber structure and film composition.

[0008]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to solve such problems, the use of a rubber-containing polymer having a specific structure results in a relatively high temperature. The present invention has been accomplished by finding that an acrylic resin film for lamination having excellent plasticizer whitening resistance can be obtained even under conditions.

That is, the present invention comprises 20 to 94.5 parts by mass of a thermoplastic polymer (I) and 5.5 to 80 parts by mass of a rubber-containing polymer (II) shown below, and (I) and ( II) is 100 parts by mass, and the ratio of the rubber polymer (II-B) in the rubber-containing polymer (II) is 5 to 72 mass% of the total of (I) and (II). It is an acrylic resin film.

Thermoplastic polymer (I): 50 to 100 mass% of methacrylic acid alkyl ester, 0 to 50 mass% of acrylic acid alkyl ester, and 0 to 49 mass% of other vinyl monomer copolymerizable therewith. And its reduced viscosity (0.1 g of the polymer was dissolved in 100 mL of chloroform,
A thermoplastic polymer having a measured value at 25 ° C.) of 0.1 L / g or less.

Rubber-containing polymer (II): The innermost layer is a hard polymer (II-A) containing a methacrylic acid alkyl ester as a main component and having a glass transition temperature of 25 ° C. or higher, and the intermediate layer is an acrylic acid alkyl ester. A three-layer structure comprising a rubber polymer (II-B) having a glass transition temperature of less than 0 ° C. as a main component and an outermost polymer (II-C) having an alkyl methacrylate as a main component as an outermost layer The value of [diameter of rubber polymer (II-B) -diameter of hard polymer (II-A)] in the rubber-containing polymer (II) observed with a transmission electron microscope is 0.07 μm. A polymer that is:

The present invention also relates to a thermoplastic polymer (I) 2
0-94.4 parts by mass, rubber-containing polymer (II) 5.5-7
9.9 parts by mass and the thermoplastic polymer (II
I) consisting of 0.1 to 10 parts by mass, the total of (I), (II) and (III) is 100 parts by mass, and the rubber polymer (II-B) in the rubber-containing polymer (II) is The ratio is (I),
It is an acrylic resin film for lamination which is 5 to 72 mass% of the total of (II) and (III).

Thermoplastic polymer (III): 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another vinyl monomer copolymerizable therewith, and its reduced viscosity (polymer 0. 1 g is dissolved in 100 mL of chloroform,
Thermoplastic polymer having a measured value at 25 ° C. of more than 0.1 L / g.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polymer (I) used in the present invention is a methacrylic acid alkyl ester 50 to 10
0% by mass, 0 to 50% by mass of alkyl acrylate, and 0 to 49% by mass of other vinyl monomer copolymerizable therewith, and its reduced viscosity (polymer 0.1 g in chloroform 100 mL). Melted and measured at 25 ° C) is 0.1
It is a polymer having L / g or less.

The reduced viscosity of the thermoplastic polymer (I) is 0.1.
It is preferably L / g or less because proper elongation occurs when the film raw material resin is melted and the film forming property becomes good.
Further, the reduced viscosity of the thermoplastic polymer (I) is 0.05 L /
It is preferably at least g. If it is higher than 0.05 L / g, the film will not be brittle, and thus the film will not easily break during film formation and printing.

As the methacrylic acid alkyl ester used in the thermoplastic polymer (I), methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like can be used, but methyl methacrylate is most preferable. These can be used alone or in combination of two or more. As the acrylic acid alkyl ester, methyl acrylate, ethyl acrylate, butyl acrylate and the like can be used. Acrylic acid alkyl ester is 0-50% by mass
Is used, preferably in the range of 0.1 to 40% by mass. These can be used alone or in combination of two or more. Examples of other copolymerizable vinyl monomers include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; various vinyl monomers such as acrylonitrile and methacrylonitrile, and cyanide vinyl compounds. These can be exemplified, and these can be used alone or in combination of two or more kinds.

The method of polymerizing the thermoplastic polymer (I) is not particularly limited, but it can be carried out by a usual method such as suspension polymerization, emulsion polymerization, bulk polymerization and the like. It should be noted that a chain transfer agent must be used in order to set the reduced viscosity within the range limited by the present invention. Although various kinds of chain transfer agents can be used, mercaptans are preferable. The amount of the chain transfer agent needs to be appropriately determined depending on the type and composition of the monomer.

The glass transition temperature of the thermoplastic polymer (I) is important, and the glass transition temperature is preferably 90 ° C. or higher. At 90 ° C. or higher, the impregnation speed of the plasticizer becomes slow, and thus the whitening resistance of the plasticizer becomes good. More preferably 1
The temperature is 00 ° C or higher.

Rubber-containing polymer (II) used in the present invention
Is a graft copolymer having a multi-layer structure, which is an important component for achieving both plasticizer whitening resistance and moldability, and which contains an acrylic acid alkyl ester as a main component of rubber.

In the rubber-containing polymer (II), the innermost layer is a hard polymer (II-A) containing a methacrylic acid alkyl ester as a main component and having a glass transition temperature of 25 ° C. or higher, and the intermediate layer is acrylic acid. A rubber polymer (II-B) containing an alkyl ester as a main component and having a glass transition temperature of less than 0 ° C., which is a polymer (II-A) and a rubber polymer (II-B). II-A + B), the outermost layer polymer containing an alkyl methacrylate as a main component as the outermost layer (II
It is a polymer having a three-layer structure grafted with -C).

As the acrylic acid alkyl ester used here, various ones may be used alone or in combination of two or more, and among them, butyl acrylate and 2-ethylhexyl acrylate are preferable. Also, as the methacrylic acid alkyl ester, various ones may be used alone or in combination of two or more, and methyl methacrylate and butyl methacrylate are preferable.

Hard polymer (II-A) and rubber polymer (II-
To obtain B), one or more of various other copolymerizable vinyl monomers can be copolymerized. The vinyl monomer used here is preferably styrene, acrylonitrile or the like. Further, in the present invention, a copolymerizable crosslinkable monomer can be used. The crosslinkable monomer 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 kinds. It is preferable to use a copolymerizable crosslinkable monomer since it is possible to reduce the whitening caused by the swelling of the rubber due to the plasticizer contained in the resin that contacts the film.

In the polymer (II-A + B), the hard polymer (II
-A) is 20 to 80% by mass, and the rubber polymer (II-B) is 8%.
It is preferably in the range of 0 to 20% by mass from the viewpoint of plasticizer whitening resistance and moldability. The hard polymer (II-A) is preferably present in an amount of 40% by mass or more in the polymer (II-A + B) from the viewpoint of the plasticizer whitening resistance, and the rubber polymer (II
-B) is more preferably present in the polymer (II-A + B) in an amount of 40% by mass or more from the viewpoint of moldability.

The hard polymer (II-A) must have a glass transition temperature in the range of 25 ° C. or higher from the viewpoint of plasticizer whitening resistance, and preferably in the range of 90 ° C. or higher. .

The monomer of the outermost layer polymer (II-C) grafted to the polymer (II-A + B) contains methacrylic acid alkyl ester as a main component, that is, 50% by mass or more of methacrylic acid alkyl ester. Those containing are used, and specific examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like, and these may be used alone or in combination of two or more. Can be used in combination. Further, the copolymerizable vinyl-based monomer can be used in a range of 50% by mass or less, and these are not particularly limited, and examples thereof include alkyl acrylates such as methyl acrylate, butyl acrylate, cyclohexyl acrylate. Esters, styrene, acrylonitrile and the like can be mentioned, and these can be used alone or in combination of two or more. The monomer mixture to be grafted is a polymer (II-A +
B) 10 to 400 parts by mass, preferably 20 to 200 parts by mass are used with respect to 100 parts by mass, and the polymerization can be carried out in at least one stage or more. When the amount of the monomer mixture to be grafted is 10 parts by mass or more based on 100 parts by mass of the polymer (II-A + B), aggregation of the polymer (II-A + B) hardly occurs and transparency is improved, which is preferable.

The outermost layer polymer (II-C) preferably has a glass transition temperature of 90 ° C. or higher from the viewpoint of plasticizer whitening resistance.

Rubber-containing polymer (II) used in the present invention
Preferably has a particle size in the range of 0.2 to 0.4 μm. Furthermore, it is preferably 0.25 to 0.35 μm. The rubber-containing polymer (II) can be produced by ordinary emulsion polymerization. When the particle diameter is 0.2 μm or more, the film obtained is not fragile with the amount of the rubber-containing polymer (II) of the present invention used, and the film formation is good. When the particle size is 0.4 μm or less, the transparency of the obtained film becomes good.

In the present invention, [rubber polymer (II-B)]
Value of diameter-hard polymer (II-A) diameter] is important, and from the viewpoint of plasticizer whitening resistance , this value is 0.07 μm.
It is in the following range, and more preferably in the range of 0.05 μm or less.

The thermoplastic polymer used in the present invention (II
I) is composed of 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another vinyl monomer copolymerizable therewith, and its reduced viscosity (polymer 0.1 g is dissolved in chloroform 100 mL). , Measured at 25 ° C.) is more than 0.2 L / g. Thermoplastic polymer (III)
By using, the film-forming property is improved, so that it is effective especially when a high level of thickness accuracy and film-forming speed are required.

The reduced viscosity of the thermoplastic polymer (III) is 0.
When the range exceeds 2 L / g, the film has good thickness accuracy. The reduced viscosity of the thermoplastic polymer (III) used is usually more than 0.2 L / g and 2 L / g or less, preferably 1.2 L / g or less.

The thermoplastic polymer used in the present invention (II
In I), examples of the vinyl-based monomer copolymerizable with methyl methacrylate include acrylic acid alkyl ester, methacrylic acid alkyl ester, aromatic vinyl compound, vinyl cyan compound, etc. The above can be used in combination. The polymerization is preferably carried out by an emulsion polymerization method, and the polymer latex produced by the emulsion polymerization method is separated and collected by various coagulants or the solid content is separated and collected by a spray dry method to obtain a polymer powder.

In the present invention, the amount of the thermoplastic polymer (III) used as necessary is preferably 0.1 to 10 parts by mass. If it is less than 0.1 part by mass, the thermoplastic polymer (II
I) The effect of improving the film-forming property by using is difficult to appear, while
When the amount exceeds 10 parts by mass, the viscosity of the resin composition becomes high, and the film-forming property and the transparency tend to be slightly lowered.

The acrylic resin film of the present invention comprises 20 to 94.5 parts by mass of the thermoplastic polymer (I) thus obtained and 5.5 to 80 parts by mass of the rubber-containing polymer (II), (I) And the total of (II) is 100 parts by mass,
It is a film in which the proportion of the rubber polymer (II-B) in the rubber-containing polymer (II) is 5 to 72 mass% of the total of (I) and (II).

When the thermoplastic polymer (III) is used, 20 to 94.4 parts by mass of the thermoplastic polymer (I),
Consisting of 5.5 to 80 parts by mass of the rubber-containing polymer (II) and 0.1 to 10 parts by mass of the thermoplastic polymer (III),
The rubber polymer (II-B) in the rubber-containing polymer (II) has a total amount of (I), (II) and (III) of 100 parts by mass.
Of the total of (I), (II) and (III) is 5 to 7
The film is 2% by mass.

The rubber-containing polymer (II) is used in the range of 5.5 to 80 parts by mass, and the ratio of the rubber polymer (II-B) in the rubber-containing polymer (II) is particularly high. 5 to 7 of the total of (I) and (II) or (I), (II) and (III)
Must be 2% by weight. If the proportion of the rubber polymer (II-B) is 5% by mass or more, the film will not become brittle,
Film formation becomes possible. The proportion of the rubber polymer (II-B) is required to be 72% by mass or less from the viewpoint of film formability.

The proportion of the rubber polymer (II-B) is preferably 50% by mass or less, more preferably 18% by mass or less, from the viewpoints of plasticizer whitening resistance and surface hardness.

The acrylic resin film of the present invention contains, if necessary, common compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers, colorants, and gloss agents. A quencher, an ultraviolet absorber, etc. may be included. In particular, from the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. The molecular weight of the ultraviolet absorber used is preferably 300 or more, and particularly preferably 400 or more. If an ultraviolet absorber having a molecular weight of less than 300 is used, it may be volatilized during vacuum molding or pressure molding in an injection molding die, causing mold stains. The type of the ultraviolet 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 Tinubin 234 manufactured by Ciba-Geigy, Asahi Denka Kogyo Adekastab LA-3 of the company
1. Specific examples of the latter include Tinuvin 1577 manufactured by Ciba Geigy.

The heat distortion temperature (measured according to ASTM D648) of the acrylic resin film of the present invention is preferably 90 ° C. or higher from the viewpoint of plasticizer whitening resistance. More preferably, it is 100 ° C. or higher.

Although the heat distortion temperature of the acrylic resin film of the present invention varies depending on the amount of the rubber-containing polymer (II) used, it mainly depends on the heat distortion temperature of the thermoplastic polymer (I) used in the present invention. Decided. The heat distortion temperature of the thermoplastic polymer (I) can be adjusted by adjusting the monomer composition of the thermoplastic polymer (I) by a known method. Depending on various conditions, for example, when using methyl acrylate as a copolymerization component, when the heat distortion temperature is 80 ° C. or higher, the content of methyl methacrylate in the thermoplastic polymer (I) is 88% by mass or higher. When the heat distortion temperature is 100 ° C. or higher, the content of methyl methacrylate in the thermoplastic polymer (I) can be adjusted to 95% by mass or higher. When the heat distortion temperature is 110 ° C. or higher, in the thermoplastic polymer (I),
It is necessary to copolymerize maleimides such as maleic anhydride and phenylmaleimide. Of course, even when the heat distortion temperature is 80 ° C. or higher and 100 ° C. or higher,
It is also possible to copolymerize maleimides such as maleic anhydride and phenylmaleimide to reduce the methyl methacrylate content.

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 calender method. From the viewpoint, the T-die method is preferable.

Further, as the laminating acrylic resin film, in order to impart a design property to a molded product, a film which is printed by an appropriate printing method is used if necessary. In this case, it is preferable to use an acrylic resin film that has been subjected to a one-sided printing treatment, and it is preferable to arrange the printing surface on the adhesive surface with the base resin at the time of molding from the viewpoint of protecting the printing surface and imparting a sense of quality. . Also, when using the color tone of the plastic that is the base material and using it as a substitute for transparent coating,
It can be used while remaining transparent. In particular, the acrylic resin film is used in applications where the color tone of the substrate is utilized in this way.
Compared to vinyl chloride and polyester films, it is superior in transparency, depth and luxury. Furthermore, a matte or colored product can be used if necessary.

The thickness of the acrylic resin film is 300 μm
It is below, and preferably 100 μm to 300 μm. When it is 100 μm or more, a sufficient depth can be obtained as an appearance of the molded product. When forming into a particularly complicated shape, sufficient thickness can be obtained by stretching. Further, when the thickness is 300 μm or less, the rigidity becomes appropriate, so that the laminating property, the secondary processability and the like become easy. It is economically advantageous in terms of weight per unit area. Further, the film-forming property is stable and the film can be easily manufactured.

In order to form a coating film having a sufficient thickness on a molded product, it is necessary to apply the coating several dozen times, which is costly and the productivity is extremely deteriorated. In the case of an acrylic laminated molded product, the acrylic resin film itself serves as a coating film, so that a very thick coating film can be easily formed, which is industrially advantageous.

The resin used as the base material of the molded article used in the present invention must be one that can be melt-bonded to the acrylic resin film, such as ABS resin, AS resin,
Examples of the resin include polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, and resins containing these as the main components.
A BS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin or a resin containing these resins as a main component is preferable, and 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 bond the acrylic resin film and the base material at the time of molding by devising the kind of the printing layer even with the base material resin such as polyolefin resin which is not heat-fused.

When the laminated molded article of the present invention is molded into a two-dimensional laminated body, a well-known method such as thermal lamination can be used for the base material which can be heat-sealed. Further, it is possible to bond the base material which is not heat-sealed via an adhesive.

In the case of molding into a three-dimensionally shaped laminate, known methods such as insert molding and in-mold molding can be used. Among these, the in-mold molding method is particularly preferable from the viewpoint of productivity.

In the in-mold molding method, after heating the acrylic resin film, vacuum molding is performed in a mold having a vacuuming function. This molding method is preferable from the viewpoints of workability and economical efficiency because the film molding and the injection molding can be performed in one step. The heating temperature is preferably equal to or higher than the softening temperature of the acrylic resin film. This depends on the thermal properties of the film or the shape of the molded product, but usually 70
℃ or above. Further, if the temperature is too high, the surface appearance is deteriorated and the releasability is deteriorated. This also depends on the thermal properties of the film or the shape of the molded product, but normally 170
It is preferably at most ° C.

As described above, when the film is given a three-dimensional shape by vacuum forming, the acrylic resin film is very advantageous since it has a high elongation at high temperature. After giving a three-dimensional shape by vacuum molding, the acrylic resin film and the base resin are melt-integrated by injection molding to obtain an acrylic laminated injection molded product.

[0049]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples. In the examples, "part" means "part by mass" and "%" means "% by mass". The abbreviations used in the examples are as follows.

MMA Methyl Methacrylate MA Methyl Acrylate BA Butyl Acrylate AMA Allyl Methacrylate St Styrene CHP Cumene Pydroperoxide NOM n-Octyl Mercaptan DOP Dioctyl Phthalate The resulting thermoplastic polymers (I), (III), rubber containing The physical properties of the polymer (II) and the film were measured by the following test methods. 1) Dissolve 0.1 g of reduced viscosity polymer of thermoplastic polymer (I) or (III) in 100 mL of chloroform,
It was measured at 5 ° C. 2) Particle size of rubber-containing polymer (II) The final particle size of the polymer latex of the rubber-containing polymer (II) obtained by emulsion polymerization was measured with a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd. , Measured by dynamic light scattering method. 3) Diameter of rubber polymer (II-B) -hard polymer (II-
Diameter of A) The obtained film-like material was cut into an appropriate size, and the section was placed in a 0.5 mass% ruthenium tetroxide aqueous solution at room temperature for 15 minutes.
The rubber polymer (II-B) portion was dyed by immersing for a time. Further, the sample was cut into a thickness of about 70 nm using a microtome and photographed with a transmission electron microscope. From this photograph, 50 randomly dyed rubber polymers (II-
B) is selected, the inner diameter and the outer diameter of each of them are calculated, and the average value of the differences is calculated as follows: Diameter of rubber polymer (II-B) -Hard polymer (II)
-A). 4) Total light transmittance and haze value of the film were evaluated according to JIS K6714. 5) Surface gloss of film The surface gloss of the film is 60 using a gloss meter (GM-26D type manufactured by Murakami Color Research Laboratory).
The surface gloss at ° was measured. 6) Film-forming property of film A film having a thickness of 100 μm was formed by the T-die method, and it was possible to form a film without breaking the film for 5 hours or more.
The case where the film was cut several times in 5 hours was designated as Δ, and the case where the sample could not be obtained due to the cutting of the film was designated as x. 7) Plasticizer Anti-whitening DOP was used as a plasticizer. Cut the flannel cloth into 1 cm ² square pieces, put them on the molded product and drop 4 drops of DOP.
After leaving it in an atmosphere of 0 ° C. for 1 day, the flannel cloth was removed and washed with a detergent, and the degree of whitening was observed.

[0051] ○ -Blanching is inconspicuous △ -Slight whitening is observed × -Blanching is observed 8) Glass transition temperature It was calculated by the FOX formula.

Example 1 a) Production of Rubber-Containing Polymer (II) Raw materials (polymer (II-A)) of (a) and (b) shown below were charged into a reaction vessel, and the mixture was heated at 80 ° C. under a nitrogen atmosphere. Polymerization was carried out for 90 minutes with stirring. Then, the raw material (rubber polymer (II-B)) of (C) was continuously added over 90 minutes, and polymerization was further performed for 120 minutes to obtain a polymer latex.

After the following raw material (d) was added to the obtained elastic polymer latex and stirred, the following raw material (e) (outermost layer polymer (II-C)) was added at 80 ° C. for 45 minutes. Added continuously over a period of 80 minutes and then an additional 80
Polymer containing rubber (II) by continuously polymerizing at ℃ for 1 hour
A latex was obtained. The rubber-containing polymer (II) thus obtained had a particle size of 0.27 μm. The rubber polymer (II-
The glass transition temperature of B) was -34 ° C.

The rubber-containing polymer (II) latex is subjected to coagulation, aggregation and solidification reaction using calcium chloride, filtration,
It was washed with water and dried to obtain a rubber-containing polymer (II) -1. (A) Deionized water 300 parts N-acyl sarcosinate 0.5 part Boric acid 1.0 part Sodium carbonate 0.1 part Sodium formaldehyde sulfoxylate 0.5 part Ferrous sulfate 0.00024 part Ethylenediaminetetraacetic acid Disodium 0.00072 parts (b) MMA 49.5 parts AMA 0.5 parts CHP 0.15 parts (c) BA 40.0 parts St 9.5 parts AMA 0.5 parts CHP 0.15 parts (d) Deionized water 5 parts N-acyl sarcosinate 1.2 parts (e) MMA 79.2 parts MA 0.8 parts NOM 0.28 parts CHP 0.24 parts b) Thermoplastic polymer (III) production reactor Then, 200 parts of ion-exchanged water substituted with nitrogen was charged, 1 part of emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. Then MMA 40 parts, BA10
Part, NOM 0.005 part, charged at 65 ° C under nitrogen atmosphere
The mixture was stirred for 3 hours to complete the polymerization. MM continues
A monomer mixture consisting of 48 parts of A and 2 parts of BA was added dropwise over 2 hours, and after completion of the addition, the mixture was maintained for 2 hours to complete the polymerization. The obtained latex was added to a 0.25% sulfuric acid aqueous solution, the polymer was acid-coagulated, then dehydrated, washed with water and dried to recover the polymer in a powder form. The reduced viscosity ηsp / c of the obtained copolymer was 0.38 L / g. c) Production of acrylic film Rubber-containing polymer (II) -1, obtained as described above,
Methyl methacrylate / methyl acrylate copolymer (methyl methacrylate / methyl acrylate = 98/2, which is the thermoplastic polymer (III) and the thermoplastic polymer (I).
The reduced viscosity of 0.06 L / g and the glass transition temperature of 104 ° C.) were mixed at various ratios shown in Table 1 using a Henschel mixer. Next, 40 mmφ screw type extruder (L /
C = 200-260 using D = 26)
℃, die temperature 250 ℃ melt kneading, pelletized,
A film composition was obtained.

The obtained pellets were dried at 80 ° C. for a whole day and night, and using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm T die, the cylinder temperature was 200 ° C. to 240 ° C. and the T die temperature was 250. A 200 μm film was formed at 0 ° C.

The acrylic film obtained was printed and processed,
After heating at 140 ° C. for 1 minute, vacuum molding was performed with a mold having a vacuuming function. With the molded film placed in a mold, the ABS resin shown in Table 2 was injection-molded on the print side of the film to obtain a molded product.

As for the film forming property, as described above, 100 μ
A film having a thickness of m was formed and judged. The film-forming properties of the obtained film are shown in Table 1, and the evaluation results of the physical properties of the film and the plasticizer whitening resistance are shown in Table 2.

Examples 2 to 4 Example 1 was repeated except that the blending amounts of the thermoplastic polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III) in the film were changed as shown in Table 1. It carried out similarly.

Example 5 A rubber-containing polymer (II obtained by polymerizing the rubber-containing polymer (II) -1 of Example 1 by changing the composition of (B) to (B) shown below (II) ) -2 was carried out in the same manner as in Example 1. (B) MMA 45.5 parts BA 4.0 parts AMA 0.5 parts CHP 0.15 parts Example 6 In the polymerization of the rubber-containing polymer (II) -1 of Example 1, the composition of (E) is as follows. Example 2 was carried out in the same manner as in Example 1 except that the rubber-containing polymer (II) -3 obtained by polymerization was used instead of the above-mentioned (e). (H ') MMA 73.6 parts BA 6.4 parts NOM 0.28 parts CHP 0.24 parts Example 7 Instead of the thermoplastic polymer (I) of Example 1, methyl methacrylate / butyl acrylate copolymerization Example 1 was carried out in the same manner as in Example 1 except that a combined product (methyl methacrylate / butyl acrylate = 92/8, reduced viscosity 0.07 L / g, glass transition temperature 84 ° C.) was used.

Comparative Examples 1 and 2 Example 1 except that the blending amounts of the thermoplastic polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III) in the film were changed as shown in Table 1. It carried out similarly.

Comparative Example 3 A rubber-containing polymer obtained by polymerizing the rubber-containing polymer (II) -1 of Example 1 by changing the composition of (B) to (B '') shown below The same procedure as in Example 1 was repeated except that II) -4 was used. (B ″) BA 40.0 parts St 9.5 parts AMA 0.5 parts CHP 0.15 parts Comparative Example 4 In the polymerization of the rubber-containing polymer (II) -1 of Example 1, (b) and (c) The composition of each is shown below (b
′) And (c ″) were used, and the same procedure as in Example 1 was carried out except that the rubber-containing polymer (II) -5 obtained by polymerization was used. (B '″) MMA 19.8 parts AMA 0.2 parts CHP 0.06 parts (ha ″) BuA 64.0 parts St 15.2 parts AMA 0.8 parts CHP 0.24 parts

[0062]

[Table 1]

[0063]

[Table 2]

From the above Examples and Comparative Examples, the following was found. The films of Examples 1 to 7 all have good film forming properties, transparency, pencil hardness, DOP whitening resistance and vacuum formability. The film having a low elastic copolymer content of Comparative Example 1 has poor film forming properties. The film having a high rubber-containing polymer content of Comparative Example 2 has a poor film-forming property. The films of Comparative Examples 3 and 4 have good film-forming properties, transparency, pencil hardness, and vacuum formability, but have poor DOP whitening resistance and are limited in industrial use. Low value.

[0065]

Industrial Applicability According to the present invention, an acrylic resin film for lamination, which has excellent plasticizer whitening resistance even when used at a relatively high temperature, and a laminate molded product of this acrylic film are obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08J 5/18 CEY C08J 5/18 CEY C08L 51/00 C08L 51/00 // B29K 105: 20 B29K 105: 20 621: 00 621 : 00 633: 04 633: 04 B29L 9:00 B29L 9:00 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 33/06-33/12 C08L 51/00-51/06 C08F 265 / 06 B32B 27/30 B29C 45/14 B29C 51/10

Claims (8)

(57) [Claims] 1. A thermoplastic polymer (I) 2 shown below.
0-94.5 parts by mass and rubber-containing polymer (II) 5.5
-80 parts by mass, and the total of (I) and (II) is 1
The amount of the rubber polymer (II-B) in the rubber-containing polymer (II) is 5 parts by weight of the total of (I) and (II).
The acrylic resin film for lamination which is 72 mass%. Thermoplastic polymer (I): Methacrylic acid alkyl ester 50 to 100 mass% and acrylic acid alkyl ester 0
.About.50% by mass and 0 to 49% by mass of another vinyl monomer copolymerizable therewith, and its reduced viscosity (polymer 0.
A thermoplastic polymer in which 1 g is dissolved in 100 mL of chloroform and measured at 25 ° C.) is 0.1 L / g or less. Rubber-containing polymer (II): The innermost layer is a hard polymer (II-A) whose main component is methacrylic acid alkyl ester and has a glass transition temperature of 25 ° C. or higher, and the intermediate layer is mainly composed of acrylic acid alkyl ester. And a rubber polymer (II-B) having a glass transition temperature of less than 0 ° C. and an outermost polymer (II-B) whose outermost layer is mainly composed of alkyl methacrylate.
-C) has a three-layer structure and is observed in a rubber-containing polymer (II) with a transmission electron microscope [diameter of rubber polymer (II-B) -of hard polymer (II-A)]. Polymer having a value of [diameter] of 0.07 μm or less. 2. A thermoplastic polymer (I) of 20 to 94.4 parts by mass, a rubber-containing polymer (II) of 5.5 to 79.9 parts by mass, and a thermoplastic polymer (III) of 0.1. 1-1
0 parts by mass, the total of (I), (II) and (III) is 100 parts by mass, and the ratio of the rubber polymer (II-B) in the rubber-containing polymer (II) is (I), (II) and (II
An acrylic resin film for lamination, which is 5 to 72 mass% of the total of I). Thermoplastic polymer (III): 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another vinyl monomer copolymerizable therewith, and its reduced viscosity (0.1 g of the polymer is chloroform. Dissolve in 100 mL, 25
A thermoplastic polymer having a measured value at 0 ° C. of more than 0.1 L / g. 3. The acrylic resin film for lamination according to claim 1, wherein the thermoplastic polymer (I) has a glass transition temperature of 90 ° C. or higher. 4. The acrylic resin film for lamination according to claim 1, wherein the glass transition temperature of the hard polymer (II-A) in the rubber-containing polymer (II) is 90 ° C. or higher. 5. The acrylic film for laminating according to claim 1, wherein the outermost layer polymer (II-C) in the rubber-containing polymer (II) has a glass transition temperature of 90 ° C. or higher. 6. An acrylic laminated molded article, which is obtained by laminating and bonding the acrylic resin film according to claim 1. 7. The acrylic laminated molded article according to claim 6, which is obtained by subjecting an acrylic film to vacuum molding or pressure molding in an injection molding die, and then injection molding a resin as a base material. 8. The acrylic laminated molded article according to claim 6, which is obtained by printing one side of an acrylic film and then laminating the printing side of the film on a resin as a base material.