JP3142774B2 - Acrylic film and acrylic laminated injection molded product using it - 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 injection molded product obtained by laminating and bonding a specific acrylic film, and an acrylic film used for producing such a molded product.

[0002]

2. Description of the Related Art As a method of decorating the surface of a plastic product, a direct printing method and a transfer method can be roughly classified. The direct printing method is a method of printing directly on a molded article, and includes pad printing, curved silk printing, electrostatic printing, etc.
It is unsuitable for producing a molded article having a complicated shape, and it is also difficult to impart a high degree of design. The transfer method includes a thermal transfer method and a water transfer method, but has 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 for imparting a design property to a molded product at low cost. This method, after printing a sheet or film of polyester resin, polycarbonate resin, acrylic resin, etc., into a three-dimensional shape by vacuum molding or the like, or without molding, insert it into an injection mold, Injection-molding a resin as a base material, there are cases where a resin sheet or film is integrated with a base resin, and cases where only printing is transferred.

On the other hand, acrylic films are used for protecting surfaces of polycarbonate, vinyl chloride, etc. due to their excellent transparency and weather resistance. However, since the thickness is 300 μm or less, it is difficult to form a film without flexibility, and there is a problem that the surface hardness is low.

For example, an acrylic resin composition having excellent transparency, weather resistance and film moldability is disclosed in Japanese Patent Application Laid-Open No. 63-779.
No. 63. However, there is no mention of the particle size of the rubber-containing polymer, and the particle size of the rubber-containing polymer obtained in the examples is 0.15 μm or less. Further, since the amount of the rubber-containing polymer added was substantially 28% by weight or more, the surface hardness was inferior.

[0006]

SUMMARY OF THE INVENTION In the in-mold molding,
When a polyester resin or a polycarbonate resin is used or when only printing is transferred, there is a defect that the appearance lacks a sense of quality and depth, and the weather resistance is also insufficient.

[0007] In order to make the surface of the molded product subjected to the design processing to have a deep or high-grade appearance, a coating step is further provided, which leads to a problem that the cost is increased. In addition, the coating process, which handles a large amount of solvent,
Workability is poor and improvement is required.

[0008] Coating requires skill of skilled workers, and in order to obtain a sufficient surface appearance with a deep and luxurious feel, it is necessary to repeat the coating several times to ten or more times in many cases. Cost and productivity is reduced.

[0009] In recent years, a coating process using a large amount of an organic solvent has become a problem from the viewpoint of improving the working environment.

[0010] On the other hand, a molded product obtained by laminating an acrylic film by in-mold molding is excellent in a sense of depth and luxury like a molded product subjected to coating treatment. However, in general, an acrylic film has insufficient surface hardness and heat resistance. However, there are drawbacks such as that the molded product is easily damaged when formed, and the surface appearance becomes poor when exposed to high temperatures.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the particle size of the rubber-containing polymer which has been conventionally used for acrylic films has been increased. The present inventors have found that an acrylic film having excellent surface hardness can be obtained by using a smaller amount of a rubber-containing polymer having a specific particle size than before, and have reached the present invention.

That is, the gist of the present invention is as follows.
0 to 10 parts by weight of the thermoplastic polymer (I), 5.5 to 25 parts by weight of the rubber-containing polymer (II) and the thermoplastic polymer (II)
I) 65 to 94.5 parts by weight, the total of (I), (II) and (III) is 100 parts by weight, and the proportion of the elastic copolymer in the rubber-containing polymer (II) is (I) ), (II) and (III) in a thickness of 5-18% by weight,
This is an acrylic film for an acrylic laminated injection molded product having a thickness of 0 μm or less.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylic film according to the present invention can be obtained as a thin film having a thickness of 300 μm or less and having good transparency, and is subjected to an operation such as crosslinking as a means for increasing the surface hardness. It is excellent in secondary workability such as stretching and bending and is most suitable for production of acrylic laminated injection molded products.

The thermoplastic polymer (I) used in the present invention
Is 50 to 100% by weight of methyl methacrylate and at least one of other vinyl monomers copolymerizable therewith.
0% by weight, and the reduced viscosity of the polymer (polymer 0.1
g in 100 mL of chloroform and measured at 25 ° C)
Is a thermoplastic polymer exceeding 0.2 L / g, and is a component for improving the film forming property. Film formation is possible without using the thermoplastic polymer (I),
Since the melt tension decreases, it is impossible to form the film without lowering the discharge amount during film formation and lowering the resin temperature, and the productivity becomes worse and the thickness unevenness of the film increases. preferable.

[0015] The reduced viscosity of the thermoplastic polymer (I) is important. If the reduced viscosity is 0.2 L / g or less, a film having good thickness accuracy cannot be obtained. The reduced viscosity of the thermoplastic polymer (I) 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 (I) used in the present invention
In the above, as a vinyl monomer copolymerizable with methyl methacrylate, an alkyl acrylate, an alkyl methacrylate, an aromatic vinyl compound, a vinyl cyanide compound and the like can be used. The polymerization is preferably performed by an emulsion polymerization method, and the polymer can be recovered in a powder form by a usual emulsion polymerization method and a post-treatment method.

The rubber-containing polymer (II) used in the present invention
Is a graft copolymer having an effect of imparting excellent impact resistance and elongation to a resin composition and having a multilayer structure containing an alkyl acrylate as a main component of rubber.

The rubber-containing polymer (II) used in the present invention
Consists of 50 to 99.9% by weight of an alkyl acrylate, 0 to 49.9% by weight of another copolymerizable vinyl monomer and 0.1 to 10% by weight of a copolymerizable crosslinkable monomer. The monomer mixture is polymerized to obtain an elastic body, and in the presence of 100 parts by weight of the obtained elastic copolymer, 50 to 100% by weight of a methacrylic acid ester and a vinyl monomer 0 to be copolymerizable therewith. Monomer consisting of 50% by weight or its mixture 1
It is obtained by polymerizing 0 to 400 parts by weight in at least one stage.

As the alkyl acrylate used herein, those having 1 to 8 carbon atoms in the alkyl group can be used, and among them, butyl acrylate, 2-ethylhexyl acrylate and the like are preferable. In obtaining the elastic copolymer, 49.9% by weight or less of another copolymerizable vinyl monomer can be copolymerized. As the vinyl monomer used here, methyl methacrylate,
Alkyl methacrylates such as butyl methacrylate and cyclohexyl methacrylate, and styrene and acrylonitrile are preferred. Further, in the present invention,
A copolymerizable crosslinkable monomer is used. The crosslinkable monomer used is not particularly limited, but is preferably ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate. , Divinylbenzene, diallyl maleate, trimethylol triacrylate, allyl cinnamate and the like, and these can be used alone or in combination of two or more.

As the monomer to be grafted onto the elastic copolymer, at least 50% by weight of methacrylate is used. Specifically, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid are used. And cyclohexyl acid. Further, 50% by weight or less of a copolymerizable vinyl monomer is used, and these are not particularly limited, but specifically, methyl acrylate, butyl acrylate,
Examples include alkyl acrylates such as cyclohexyl acrylate, styrene and acrylonitrile.
The monomer mixture to be grafted is 10 to 400 parts by weight, preferably 20 to 2 parts by weight, based on 100 parts by weight of the elastic copolymer.
00 parts by weight are used, and the polymerization can be carried out in at least one stage. If the amount of the monomer mixture to be grafted is less than 10 parts by weight with respect to 100 parts by weight of the elastic copolymer, the transparency is deteriorated due to aggregation of the elastic copolymer, which is not preferable.

The rubber-containing polymer (II) used in the present invention
Has a particle diameter of 0.2 to 0.4 μm, preferably 0.25 to 0.35 μm. The rubber-containing polymer (II) can be obtained by ordinary emulsion polymerization. Particle size 0.2
If it is less than μm, the film obtained becomes brittle with the use amount of the rubber-containing polymer (II) of the present invention, and film formation becomes impossible. When the particle diameter exceeds 0.4 μm, the transparency of the obtained film is deteriorated.

The thermoplastic polymer (II) used in the present invention
I) includes 50 to 100% by weight of a methacrylate having an alkyl group having 1 to 4 carbon atoms, 0 to 50% by weight of an acrylate, and at least one other vinyl monomer copolymerizable therewith. 0 to 49% by weight, and the reduced viscosity of the polymer (0.1 g of the polymer in 100 mL of chloroform)
(Measured at 25 ° C.) is 0.1 L / g or less. The reduced viscosity of the thermoplastic polymer (III) is 0.
If it exceeds 1 L / g, the melt viscosity of the film raw material resin becomes too high, resulting in poor film-forming properties. Further, the reduced viscosity of the thermoplastic polymer (III) is preferably at least 0.05 L / g. When it is lower than 0.05 L / g, the film becomes too brittle, and the film tends to break during film formation and printing.

As the methacrylate used in the thermoplastic polymer (III), methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like can be used, and methyl methacrylate is most preferred. As the acrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the like can be used. The acrylate is in the range of 0 to 50% by weight, preferably 0.1 to 40% by weight.
Used in the range of weight percent. Known monomers can be used as other copolymerizable vinyl monomers.

The method for polymerizing the thermoplastic polymer (III) is not particularly limited, but it can be a conventional method such as suspension polymerization, emulsion polymerization, or bulk polymerization. It is necessary to use a chain transfer agent in order to limit the viscosity in the present invention. Known chain transfer agents can be used,
Preferred are mercaptans. The amount of chain transfer agent is
It is necessary to appropriately determine the type and composition of the monomer.

The acrylic film of the present invention is a film comprising the thermoplastic polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III) thus obtained.

In the present invention, the thermoplastic polymer (I) is used in an amount of 0 to 10 parts by weight. Film formation is possible without using the thermoplastic polymer (I),
In order to obtain sufficient film formability, it is preferable to use the compound in an amount of 0.1 part by weight or more. If the amount exceeds 10 parts by weight, the viscosity of the resin composition becomes too high, so that the film-forming property is deteriorated and the transparency is deteriorated.

The rubber-containing polymer (II) is used in an amount of 5.5 to 25 parts by weight. In particular, the proportion of the elastic copolymer in the rubber-containing polymer (II) depends on the proportion of the polymers (I), (II) and (II). It must be from 5 to 18% by weight of the total of (III). If the proportion of the elastic copolymer is less than 5% by weight, the film becomes brittle and cannot be formed. 18% by weight of elastic copolymer
If it exceeds, the transparency of the film deteriorates and the surface hardness also decreases.

The acrylic film of the present invention may contain, if necessary, a general compounding agent such as a stabilizer, a lubricant, a processing aid,
It may contain a plasticizer, an impact aid, a foaming agent, a filler, a colorant, a matting agent, an ultraviolet absorber and the like. In particular, from the viewpoint of protecting the substrate, it is preferable that an ultraviolet absorber is added 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 volatilize during vacuum molding or air pressure molding in an injection mold, causing mold contamination. The type of the ultraviolet absorber is not particularly limited, but a benzotriazole-based compound having a molecular weight of 400 or more or a triazine-based compound having a molecular weight of 400 or more can be particularly preferably used. Specific examples of the former include Tinuvin 234 of Ciba-Geigy, Asahi Denka Kogyo ADK STAB LA-3
1. Specific examples of the latter include Tinuvin 1577 manufactured by Ciba-Geigy.

The heat distortion temperature (measured based on ASTM D648) of the acrylic film of the present invention is preferably 80 ° C. or higher. When the heat distortion temperature is less than 80 ° C,
When the acrylic laminated molded article is heated, surface roughness may occur due to residual stress. Furthermore, when used for vehicle applications, if the heat deformation temperature is 100 ° C or higher, it can be used near the handle part, and if it is 110 ° C or more, it can be used near the meter panel part. More preferred.

The heat deformation temperature of the acrylic film of the present invention depends on the amount of the rubber-containing polymer (II) used, but is mainly determined by the heat deformation temperature of the thermoplastic polymer (III) used in the present invention. . The heat distortion temperature of the thermoplastic polymer (III) can be adjusted by adjusting the monomer composition of the thermoplastic polymer (III) by a known method.
Although it depends on various conditions, for example, when methyl acrylate is used as a copolymer component, the heat distortion temperature is 8
When the temperature is 0 ° C. or higher, a thermoplastic polymer (III)
The content of methyl methacrylate in the content is 88% by weight or more,
When the heat distortion temperature is 100 ° C. or higher, the methyl methacrylate content in the thermoplastic polymer (III) is 95%.
It can be adjusted by adjusting it to not less than% by weight. When the heat distortion temperature is 110 ° C. or higher, it is necessary to copolymerize maleimides such as maleic anhydride and phenylmaleimide in the thermoplastic polymer (III). Of course, even when the heat distortion temperature is 80 ° C. or higher and 100 ° C. or higher, it is possible to reduce the methyl methacrylate content by copolymerizing maleimides such as maleic anhydride and phenylmaleimide.

As a method for producing the acrylic film used in the present invention, any method such as a melt casting method, a melt extrusion method such as a T-die method and an inflation method, and a calendar method may be used. In view of this, the T-die method is preferred.

As an acrylic film as a substitute for painting, a film which is printed by an appropriate printing method as necessary to give a design property to a molded product is usually used. In this case, it is preferable to use an acrylic film that has been subjected to a one-sided printing process, and it is preferable to dispose 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. In addition, when utilizing as a substitute for a transparent coating by making use of the color tone of the plastic serving as the base material, it can be used while being transparent. In particular, for applications utilizing the color tone of the base material, an acrylic film is
Compared to vinyl chloride and polyester films, they are superior in transparency, depth and luxury.

Further, if necessary, matting or coloring can be used.

The thickness of the acrylic film is 300 μm or less, preferably 100 μm to 300 μm. 1
If the thickness is less than 00 μm, a sufficient depth cannot be obtained as a molded product appearance. Particularly when forming into a complicated shape, a sufficient thickness cannot be obtained by stretching. Further, when the thickness is more than 300 μm, the rigidity is increased, so that the laminating property, the secondary processing property, etc. are deteriorated and the film cannot be used. In addition, the weight per unit area increases, which is economically disadvantageous. Further, it is difficult to form a film, and a film cannot be stably manufactured. Further, when the thickness is 300 μm or less, the means for nipping with a metal roll used in the production of an acrylic sheet and transferring the surface to improve the transparency cannot be used because the distance between the metal rolls is too narrow. It is necessary to use a specific amount of the rubber-containing polymer having a specific particle size according to the present invention.

In order to form a coating film having a sufficient thickness by coating a molded product, over-coating is required ten and several times, which is costly and productivity is extremely deteriorated. In the case of an acrylic laminated molded product, since the acrylic film itself becomes a coating film, a very thick coating film can be easily formed, which is industrially advantageous.

The resin constituting the base material of the injection-molded article used in the present invention must be capable of being melt-bonded to an acrylic film, and may be made of ABS resin, AS resin,
A styrene resin, a polycarbonate resin, a vinyl chloride resin, an acrylic resin, a polyester-based resin or a resin containing these as a main component is mentioned.
S resin, AS resin, polycarbonate resin, vinyl chloride resin or a resin containing these resins as a main component is preferable, and an ABS resin, a polycarbonate resin or a resin containing these as a main component can be used.

Next, a method for producing the molded article of the present invention will be described.

After heating the acrylic film, vacuum forming is performed in a mold having a vacuuming function. This method is preferable from the viewpoints of workability and economical efficiency, since film molding and injection molding can be performed in one step. The heating temperature is desirably equal to or higher than the temperature at which the acrylic film softens.
This depends on the thermal properties of the film or the shape of the molded product, but is usually 70 ° C. or higher. On the other hand, if the temperature is too high, the surface appearance deteriorates and the releasability deteriorates. This also depends on the thermal properties of the film or the shape of the molded product, but is usually preferably 170 ° C. or lower.

As described above, when a three-dimensional shape is imparted to a film by vacuum forming, the acrylic film is very advantageous because it has high elongation at high temperatures.

After giving a three-dimensional shape by vacuum forming, the acrylic film and the base resin are melted and integrated by injection molding.

[0041]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the examples, “parts” represents “parts by weight”, and “%” represents “% by weight”. Abbreviations in the examples are as follows.

Methyl methacrylate MMA Methyl acrylate MA Butyl acrylate BuA 1,3 Butylene glycol dimethacrylate BD Allyl methacrylate AMA Styrene St Ethyl acrylate EA Cyclohexylmaleimide CHMA Cumene dropperoxide CHP n-octyl mercaptan NOM The obtained thermoplasticity The physical properties of the coalesced (I), the thermoplastic polymer (III), the rubber-containing polymer (II) and the film were measured by the following test methods.

1) Thermoplastic polymers (I) and (III)
0.1 g of the polymer was dissolved 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 determined by using a light scattering photometer DLS- manufactured by Otsuka Electronics Co., Ltd. The measurement was carried out by a dynamic light scattering method using No. 700.

3) Total light transmittance and haze value of the film The film was evaluated according to JIS K6714.

4) Surface Gloss of Film The surface gloss of the film was measured using a gloss meter (Model GM-26D manufactured by Murakami Color Research Laboratory).
The surface gloss at 60 ° was measured.

5) Pencil hardness of the molded article The pencil hardness was evaluated according to JIS K5400.

6) Film-forming properties A film having a thickness of 100 μm was formed by the T-die method.
も の indicates that the film was cut several times in time, and × indicates that the sample could not be obtained due to the cut of the film.
And

7) Adhesion of Film The adhesion between the film of the in-mold molded product and the injection-molded resin was evaluated by a cross-cut peeling test according to JIS K5400. did.

8) Heat Deformation Temperature of Film Composition Film composition pellets are subjected to ASTM D by injection molding.
Formed into heat deformation temperature measurement specimen based on 648, 80 ° C
After annealing for 24 hours at low load (4.6 kg / cm2)
Measured according to ASTM D648.

9) Heating test of molded product The in-mold molded product was heated at 80 ° C, 100 ° C and 110 ° C.
The film was heated in a heating furnace at a temperature of 24 ° C. for 24 hours. After cooling, the surface on which the film was laminated was smooth and unchanged from before heating.

10) Weather Resistance of In-Mold Molded Product Using an eye super UV tester (metal halide lamp type manufactured by Dainippon Plastics Co., Ltd.), the film was irradiated with ultraviolet light at an intensity of 100 mw / cm 2 from the laminated surface of the film, and the discoloration was measured.

(Examples 1, 2, 5, 6, 10, 11, 1)
4, 19, Comparative Examples 1, 3 to 5) a) Production of thermoplastic polymer (I) A reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and 1 part of potassium oleate and 0.1 part of potassium persulfate were used as emulsifiers. I put in three parts. Then, 40 parts of MMA,
10 parts of BuA and 0.005 part of NOM were charged and stirred at 65 ° C. for 3 hours under a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of MMA and 2 parts of BuA was added dropwise over 2 hours.
The time was maintained to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, and the polymer was subjected to acid coagulation, followed by dehydration, washing and drying, and the polymer was recovered in powder form.
The reduced viscosity ηsp / c of the obtained copolymer is 0.38 L /
g.

B) Production of Rubber-Containing Polymer (II) A reaction vessel was charged with a raw material comprising the following (a) and a half amount of (b), and polymerized while stirring at 80 ° C. for 90 minutes in a nitrogen atmosphere. . Next, the remaining half of the raw material (b)
It was added continuously over 0 minutes, and polymerization was further performed for 120 minutes to obtain an elastic latex.

The following raw material (c) was subsequently added to the obtained elastic latex, and after stirring, the following raw material (d) was continuously added at 80 ° C. for 45 minutes. Polymerization was carried out continuously at 80 ° C. for 1 hour to obtain a rubber-containing polymer (II) latex. The particle size of the obtained rubber-containing polymer (II) was 0.29 μm.

The rubber-containing polymer (II) latex was subjected to coagulation, coagulation and solidification reactions using calcium chloride, followed by filtration, washing with water and drying to obtain a rubber-containing polymer (II).

(A) Deionized water 300 parts N-acyl sarcosine acid 0.5 parts Boric acid 1.0 parts Sodium carbonate 0.1 parts Sodium formaldehyde sulfoxylate 0.5 parts Ferrous sulfate 0.00024 parts Ethylenediamine Disodium tetraacetate 0.00072 parts (b) BuA 80.0 parts St 19.0 parts AMA 1.0 part CHP 0.3 parts (c) Deionized water 5 parts N-acyl sarcosine acid 1.2 parts (d) 76.6 parts of MMA 3.2 parts of EA 0.28 parts of NOM 0.24 parts of CHP (c) Production of acrylic film The thermoplastic polymer (I) and the rubber-containing polymer (II) obtained as described above. And a thermoplastic polymer (III), methyl methacrylate / methyl acrylate copolymer A (methyl methacrylate / methyl acrylate = 98/2, reduced viscosity of 0. Using 6L / g) at a ratio shown in Table 1, were mixed by a Henschel mixer. Next, using a 40 mmφ screw type extruder (L / D = 26), the mixture was melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C., and pelletized to obtain a film composition.

The obtained pellets were dried at 80 ° C. for 24 hours, and a cylinder temperature of 200 ° C. to 240 ° C. and a T die temperature of 250 ° C. were used using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm T die.
Films of various thicknesses shown in Table 2 were formed at ° C.

The obtained acrylic films having various thicknesses were printed, heated at 140 ° C. for 1 minute, and then vacuum-molded with a mold having a vacuuming function. With the formed film placed in a mold, the ABS resin shown in Table 3 was injection molded on the printing surface side to obtain a molded product.

Regarding the film forming property, as described above, 100
A film having a thickness of μm was formed and judged.

Table 1 shows the film forming properties and the like of the obtained film, and Table 2 shows the evaluation results of the physical properties of the film and the surface hardness and adhesion of the molded product.

From Example 6, it can be seen that when the film thickness is small, the color depth is inferior and lacks a sense of quality.

In Example 19, since the thermoplastic polymer (I) was not used, the film-forming property was poor, and the film could not be formed unless the T-die temperature was lowered by 10 ° C. In addition, since the thickness unevenness was large, the obtained molded product was somewhat lacking in luxury.

From Comparative Example 1, it can be seen that when the amount of the rubber-containing polymer (II) used is less than 5.5 parts, the film-forming properties deteriorate.

From Comparative Example 3, the thermoplastic polymer (I)
It can be seen that use of more than 0 parts deteriorates the transparency.

From Comparative Example 4, it can be seen that when the thermoplastic polymer (III) is not used, the melt viscosity increases and the film forming property deteriorates.

According to Comparative Example 5, when the amount of the rubber-containing polymer (II) used exceeds 25 parts and the ratio of the elastic copolymer to the whole exceeds 18%, the transparency and the surface hardness may deteriorate. Understand.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

(Examples 3, 4, 7 to 9, 12, 13) Example 2 was repeated except that the resin to be injection-molded was changed to the resin shown in Table 3.
An in-mold molded product was obtained in the same manner as described above. However, when the polycarbonate resin was used, the film was not printed. Table 2 shows the evaluation results of the obtained molded product, such as surface hardness and adhesion.

Although a molded product having good appearance was obtained for all the products, those using PP, PPE or PA as the injection molding resin lacked the adhesiveness of the film.

(Examples 15 and 16, Comparative Examples 2 and 6) Except that the amount of the N-acyl sarcosinate of the raw material (a) was changed to the amount shown in Table 4 in the production of the rubber-containing polymer (II), Polymerization was carried out in the same manner as in Example 2. Table 4 shows the particle size of the obtained rubber-containing polymer (II). Using the obtained rubber-containing polymer (II), mixing with the thermoplastic polymers (I) and (III), pelletizing, film formation, printing, and vacuum forming were performed in the same manner as in Example 2. Thereafter, the ABS resin was in-mold molded into a film. Tables 1 and 2 show the film forming property of the obtained film and the physical properties of the molded product, respectively.

The particle diameter of the rubber-containing polymer (II) is 0.2 μm.
If it is less than m, even if the amount of the rubber-containing polymer (II) used is within the range specified in the present invention, as shown in Comparative Example 2, the film-forming properties deteriorate due to insufficient film strength, while When the amount of the polymer (II) used is larger than that specified in the present invention, as is apparent from Comparative Example 6, the film formability and transparency are good, but the surface hardness is remarkably deteriorated.

[0075]

[Table 4]

(Examples 17 and 18) Rubber-containing polymer (I)
In the production of I), polymerization was carried out in the same manner as in Example 1 except that the following raw material (e) was used instead of the raw material (d). The particle size of the obtained rubber-containing polymer (II) is 0.2
It was 6 μm. Using the obtained rubber-containing polymer (II), mixing with the thermoplastic polymers (I) and (III), pelletizing, film forming, printing and vacuum forming were carried out in the same manner as in Example 2. After that, the ABS resin was in-mold molded into a film. Tables 1 and 2 show the film forming property of the obtained film and the physical properties of the molded product, respectively.

(E) MMA 38.4 parts EA 1.6 parts NOM 0.14 parts CHP 0.12 parts (Examples 20 to 23) Except that thermoplastic polymer (III) was changed to that shown in Table 5 Was obtained in the same manner as in Example 2. However, in Example 23, the thermoplastic polymer (III) having a reduced viscosity of 0.04 L / g was used. However, the obtained film was brittle, and the film was cut during printing, and printing was impossible. Did not do. From the above, it can be seen that if the reduced viscosity of the thermoplastic polymer (III) is not more than 0.05 L / g, the film becomes brittle, the film forming property is deteriorated, and the film is broken during printing. Tables 1 and 2 show the film forming property of the obtained film and the physical properties of the molded product, respectively.

Table 6 shows the results of the heating test of the obtained molded product together with Example 2. It can be seen that the thermal deformation temperature at low load and the surface abnormality due to heating almost correspond.

[0079]

[Table 5]

[0080]

[Table 6]

(Examples 24 to 27) In-mold molded products were obtained in the same manner as in Example 3 except that the following various ultraviolet absorbents were added to the film composition 1 used in Example 1 and the like.

Tinuvin P Benzotriazole-based ultraviolet absorber manufactured by Ciba Geigy, Inc. Molecular weight: 225 Tinuvin 234 Benzotriazole-based ultraviolet absorber manufactured by Ciba-Geigy Inc. Molecular weight: 448 Tinuvin 1577 Triazine-based ultraviolet absorber manufactured by Ciba-Geigy Inc. Agent Molecular weight 326 Table 1 and Table 2 show the film forming property of the obtained film and the physical properties of the molded product, respectively.

In Example 24 using Tinuvin P, mold contamination due to Tinuvin P occurred during injection molding.
Due to the dirt, the sense of quality was impaired. With the other three types of ultraviolet absorbers, mold stains did not occur, indicating that the molecular weight of the ultraviolet absorber is important.

Table 7 shows the results of the weather resistance test of the obtained molded product together with Example 3. This shows that the benzophenone-based ultraviolet absorber cannot impart sufficient weather resistance to the acrylic film of the present invention.

[0085]

[Table 7]

[0086] For all the film compositions,
An attempt was made to form a film having a thickness of 500 μm, but none of the films could be formed stably.

[0087]

According to the present invention, it is possible to obtain an injection-molded article having a coating with a sufficient thickness at a low cost and easily, and having an excellent surface appearance and a sense of depth.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI C08L 51:00) B29K 33:04 55:02 69:00 B29L 9:00 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08J 5/18 CEY B29C 45/14 B32B 27/30 C08L 33/06 CA (STN)

Claims (10)

(57) [Claims] 1. A thermoplastic polymer (I) 0 shown below
10 to 10 parts by weight, 5.5 to 25 parts by weight of the rubber-containing polymer (II) and 65 to 94.5 parts by weight of the thermoplastic polymer (III), and the total of (I), (II) and (III) Is 10
0 parts by weight, and the proportion of the elastic copolymer in the rubber-containing polymer (II) is 5 to 5 of the total of (I), (II) and (III).
An acrylic film for an acrylic laminated injection molded product having a thickness of 300 μm or less, which is 18% by weight. Thermoplastic polymer (I) Consists of 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of at least one other vinyl monomer copolymerizable therewith, and the reduced viscosity of the polymer (polymer 0.1 g is dissolved in 100 mL of chloroform and measured at 25 ° C.) to exceed 0.2 L / g. Rubber-containing polymer (II) 50 to 99.9% by weight of alkyl acrylate, 0 to 49.9% by weight of other copolymerizable vinyl monomer and 0.1 to 0.1% of copolymerizable crosslinkable monomer 100 parts by weight of an elastic copolymer consisting of 10% by weight is mixed with
100% by weight and a copolymerizable vinyl monomer 0
To 50 % by weight of a monomer or a mixture thereof
A rubber-containing copolymer having 400 parts by weight of a bound polymer and a particle size of 0.2 μm to 0.4 μm. Thermoplastic polymer (III) 50 to 100% by weight of a methacrylate having an alkyl group having 1 to 4 carbon atoms, and 0 to 50% of an acrylate
% By weight and at least one type of another vinyl monomer copolymerizable therewith in the range of 0 to 49% by weight. The reduced viscosity of the polymer (0.1 g of the polymer dissolved in 100 mL of chloroform, (Measurement) is 0.1 L / g or less. 2. The acrylic film according to claim 1, which has a pencil hardness of H or higher. 3. A thermoplastic polymer (I) having a content of 0.1
The acrylic film according to claim 1, wherein the amount is not less than part by weight. 4. The acrylic film according to claim 1, comprising 0.1 to 5% by weight of an ultraviolet absorber. 5. The acrylic film according to claim 1, which has a heat distortion temperature (measured according to ASTM D648) of 80 ° C. or higher. 6. When cooling and solidifying a thermoplastic resin mixture in a molten state, one metal roll is simultaneously held without being pinched by two metal rolls, thereby being not regulated in thickness and surface transferred. The acrylic film according to claim 1, wherein the acrylic film is in contact with only the resin and has been cooled and solidified. 7. An acrylic laminated injection-molded article obtained by laminating and bonding the acrylic film according to claim 1. 8. The acrylic laminated injection-molded article according to claim 7, which is obtained by subjecting an acrylic film to vacuum molding or air-pressure molding in an injection mold, and then subjecting a resin as a base material to injection molding. 9. The acrylic injection molded article according to claim 7, wherein the resin constituting the base material constituting the injection molded article is an ABS resin, a polycarbonate resin or a resin containing these as a main component. 10. The acrylic laminated injection-molded article according to claim 8, which is obtained by printing on one side of an acrylic film and then laminating a resin serving as a base material on the printed surface side.