JP2002080678A - Acrylic resin film for coating substitute and acrylic laminate molding prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic resin film for a coating substitute which is excellent in clarity and whitening resistance in molding and which is suitable for in-mold molding; and an acrylic laminate molding. SOLUTION: This acrylic resin film comprises (I) 20-94.5 pts. thermoplastic polymer containing 50-100% MMA units and having a reduced viscosity of 0.1 L/g or lower and (II) 5.5-80 pts. rubber-containing polymer obtained by the graft polymerization of MMA in the presence of (II-A) an elastic BA polymer to form (II-B) a hard polymer, provided that the sum of polymer (I) and polymer (II) being 100 pts. and that polymer (II) contains 5-72 pts. polymer (II-A). The average particle size of polymer (II) is lower than 0.2 μm. The acrylic laminate molding is prepared by laminating the resin film to a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin film used as a substitute for painting and having excellent moldability and an acrylic laminated molded product using the same.

[0002]

2. Description of the Related Art As a method of decorating the surface of a plastic product, there are roughly two methods: a direct printing method and a transfer method. The direct printing method is a method of printing directly on a molded article, and includes a pad printing method, a curved silk printing method, an electrostatic printing method, and the like. These are unsuitable for the production of a molded article having a complicated shape, and it is also difficult to impart a high degree of design. On the other hand, 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, This is a method of injection molding a resin as a base material. In in-mold molding, there are a case where a resin sheet or a film and a base resin are integrated, and a case where only printing is transferred. Acrylic resin films having excellent surface hardness and heat resistance that can be used for in-mold molding are disclosed in JP-A-8-323934 and JP-A-11-14.
No. 7237 and the like. Such an acrylic resin film is used not only for imparting decorative properties to a molded product but also as a substitute material for clear coating.

[0004] Japanese Patent Application Laid-Open No. 8-267500 discloses an acrylic resin film having a high processability and flexibility, comprising a rubber-containing multi-layered polymer which can be used for in-mold molding.

[0005]

Problems to be Solved by the Invention
No. 4, JP-A-11-147237 discloses that an acrylic resin having excellent surface hardness, heat resistance and transparency can be obtained by using a small amount of a rubber-containing polymer having a relatively large particle diameter. Has been described. However, especially when applied to an application in which moldability is important, the amount of the rubber-containing polymer in the film is inevitably increased. There is a problem of lowering.

[0006] In particular, in the case of a substitute for painting, in many cases, the acrylic resin film is printed, the printed surface is attached to the base material side, and the acrylic resin film is used in a state where the acrylic resin film is on the outside. Therefore, industrially, the transparency of an acrylic resin film used as a substitute for clear coating is very important.

In in-mold molding, it is effective to shorten the preheating time during vacuum molding in order to increase the molding cycle. However, conventionally known coating substitute films have particles of rubber-containing polymer. Since the diameter is relatively large, there is a problem that when molded by shortening the heating time, the whitening resistance is necessarily inferior to that of a rubber having a small particle diameter. Furthermore, from the viewpoint of energy efficiency, it is preferable that the preheating temperature during vacuum molding is lower, but for rubber having a relatively large particle diameter, molding was performed at a lower heating temperature, as in the case where the heating time was shortened. Also in this case, there is a problem that the whitening resistance is necessarily inferior to that of the small particle size rubber.

On the other hand, the acrylic resin film disclosed in Japanese Patent Application Laid-Open No. 8-267500 is rich in processability and flexibility, and has good in-mold moldability. However, since the rubber portion and the matrix polymer portion are simultaneously polymerized to form a film, only one type of acrylic resin film can be obtained from one multilayer structure polymer. Therefore, for example, there is a problem that it is not possible to quickly respond to various needs that increase in response to the expansion of the market, such as designing an acrylic resin film having optimal moldability for each laminated molded product.

Further, Japanese Patent Application Laid-Open No. 8-267500 discloses the use of an acrylic resin film disclosed in Japanese Patent Application Laid-Open No. 63-77963. However, Japanese Patent Application Laid-Open No. 63-77663 does not disclose a particle diameter of a rubber-containing polymer required for a coating substitute film having excellent transparency and moldability.

[0010] An object of the present invention is to solve these problems of the prior art, and specifically, an acrylic resin film which is excellent in transparency and molding whitening resistance and is particularly suitable for in-mold molding, And an acrylic laminated molded product using the same.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have identified a rubber-containing polymer having a specific particle size and a specific thermoplastic polymer. The present inventors have found that an acrylic resin film containing the same in an amount as described above has an extremely excellent effect, and have completed the present invention.

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. The amount of the elastic polymer (II-A) in (II) is 5 to 72.
It is an acrylic resin film as a substitute for coating, characterized in that the amount is 100 parts by mass [total 100 parts by mass of component (I) and component (II)]. Thermoplastic polymer (I) alkyl methacrylate 50 to 100% by mass;
It is composed of 0 to 50% by mass of an alkyl acrylate and 0 to 49% by mass of another vinyl monomer copolymerizable therewith. The reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 mL of chloroform, 0.1 L / g at 25 ° C)
The following thermoplastic polymers. Rubber-Containing Polymer (II) In the presence of an elastic polymer (II-A) having one or more layers, which is an inner layer obtained by polymerizing a monomer containing an alkyl acrylate, methacrylic acid Average particle size having a multilayer structure of two or more layers obtained by graft-polymerizing a monomer containing an alkyl ester to form a hard polymer (II-B) having one or two or more layers as an outer layer Rubber-containing polymer of less than 0.2 μm.

Further, the present invention relates to a thermoplastic polymer (I) in an amount of 10 to 94.4 parts by mass and the rubber-containing polymer (I).
I) 5.5 to 80 parts by mass of the thermoplastic polymer (III) shown below and 0.1 to 10 parts by mass of the elastic polymer (II-A) in the rubber-containing polymer (II). 5) to 7)
2 parts by mass [component (I), component (II) and component (III)
In total of 100 parts by mass]. A thermoplastic polymer (III) comprising 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another vinyl monomer copolymerizable therewith;
Reduced viscosity of polymer (0.1 g of polymer
A thermoplastic polymer having a solubility in 0 mL and measured at 25 ° C.) of more than 0.2 L / g.

Further, the present invention is an acrylic laminated molded article characterized by laminating the acrylic resin film on a substrate.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polymer (I) used in the present invention has an alkyl methacrylate of 50 to 100.
Mass%, and alkyl acrylate 0 to 50 mass%
And 0 to 49% by mass of another vinyl monomer copolymerizable therewith, and the reduced viscosity of the polymer (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is 0.1 L. / G or less of a thermoplastic polymer.

The reduced viscosity of the thermoplastic polymer (I) is 0.1
When the content is not more than L / g, an appropriate elongation occurs when the film raw material resin is melted, and the film forming property is improved. The lower limit of the reduced viscosity is preferably 0.05 L / g or more. At 0.05 L / g or more, the problem of film breakage during film formation and printing due to the brittleness of the film hardly occurs.

Examples of the alkyl methacrylate used for the thermoplastic polymer (I) include methyl methacrylate,
Examples include ethyl methacrylate and butyl methacrylate. Of these, methyl methacrylate is most preferred. The methacrylic acid alkyl ester is used in the range of 50 to 100% by mass.

Examples of the alkyl acrylate used as necessary for the thermoplastic polymer (I) include methyl acrylate, ethyl acrylate and butyl acrylate. The alkyl acrylate is used in the range of 0 to 50% by mass, preferably 0.1 to 40% by mass.

As other copolymerizable vinyl monomers used as necessary for the thermoplastic polymer (I), various conventionally known monomers can be used. Other vinyl monomers are used in the range of 0 to 49% by mass.

The thermoplastic polymer (I) is obtained by polymerizing these monomers. The polymerization method is not particularly limited, and the polymerization can be performed by suspension polymerization, emulsion polymerization, bulk polymerization, or the like. In order to keep the reduced viscosity of the polymer within a predetermined range, a chain transfer agent may be used. Various conventionally known chain transfer agents can be used, and mercaptans are particularly preferable. It is necessary to appropriately determine the amount of the chain transfer agent to be used depending on the type and composition of the monomer.

The rubber-containing polymer (II) used in the present invention comprises:
It is an important component for the transparency of the film and the resistance to whitening during molding, and is preferably a graft copolymer having a multilayer structure containing an alkyl acrylate as a main component of rubber.

Specifically, the rubber-containing polymer (II) is an elastic polymer (II) having a structure of one or more inner layers obtained by polymerizing a monomer containing an alkyl acrylate. In the presence of -A), a hard polymer (II-) having a structure of one or two or more outer layers by graft polymerization of a monomer mainly composed of an alkyl methacrylate is used.
A rubber-containing polymer having a multilayer structure of two or more layers and having an average particle diameter of less than 0.2 μm, which is formed by B).

As the alkyl acrylate used for the elastic polymer (II-A), various conventionally known acrylates can be used. Particularly, butyl acrylate, 2-ethylhexyl acrylate and the like are preferable. The amount of the acrylic acid alkyl ester used is preferably 35 to 100 in monomers other than the crosslinkable monomer used for the elastic polymer (II-A).
%, More preferably 50 to 100% by mass. The lower limits of these ranges are significant in terms of whitening resistance to molding and the like.

In obtaining the elastic polymer (II-A),
Other vinyl monomers copolymerizable with the alkyl acrylate can be copolymerized. Other vinyl monomers include methyl methacrylate, butyl methacrylate,
Preferred are alkyl methacrylates such as cyclohexyl methacrylate, styrene, acrylonitrile and the like.
These can be used alone or in combination of two or more. The amount of the other vinyl monomer to be used is preferably 65% by mass or less in the monomers other than the crosslinkable monomer used for the elastic polymer (II-A).

In order to obtain the elastic polymer (II-A), usually, a crosslinkable monomer is further used. The crosslinkable monomer is not particularly limited, but 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. These can be used alone or in combination of two or more. The amount of the crosslinkable monomer used is preferably 0.1 to 100 parts by mass of the monomer other than the crosslinkable monomer used for the elastic polymer (II-A).
10 parts by mass. From the viewpoint of molding whitening resistance, 0.3 parts by mass or more is more preferable. Even if the amount exceeds 10 parts by mass, there is no particular problem in physical properties, but the effect of the increase with the increase in the amount is small.

The elastic polymer (II-A) may have a structure of one layer or two or more layers. When having a structure of two or more layers, the amount of the alkyl acrylate as a whole of the elastic polymer (II-A) is preferably 35% by mass or more,
50 mass% or more is more preferable.

When a hard core structure is used, the content of the first layer alkyl acrylate may be 35% by mass or less. For example, a multilayer polymer having a hard core structure having an average particle diameter of less than 0.2 μm as described in JP-A-7-149994 can be used, although it is not described to be used for a substitute for painting.

The hard polymer (II-B) as the outer layer is formed by graft polymerization of a monomer containing an alkyl methacrylate in the presence of the elastic polymer (II-A). The hard polymer (II-B) can be obtained by polymerization in at least one stage, and can have a structure of one layer or two or more layers.

The amount of the alkyl methacrylate used is preferably 50% by mass or more of the monomers used for the hard polymer (II-B). Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and the like.

In obtaining the hard polymer (II-B),
Other vinyl monomers copolymerizable with the alkyl methacrylate can be used in combination. Other vinyl monomers include methyl acrylate, butyl acrylate, alkyl acrylates such as cyclohexyl acrylate, styrene,
Acrylonitrile and the like can be mentioned. These can be used alone or in combination of two or more. The amount of other vinyl monomers used is determined by the hard polymer (II-
In the monomer used in B), it is preferably at most 50% by mass.

The hard polymer (II-B) is an elastic polymer (II
-A) It is preferably from 10 to 400 parts by mass, more preferably from 20 to 200 parts by mass, per 100 parts by mass. The lower limits of these ranges are significant from the viewpoint of preventing deterioration of transparency due to aggregation of the elastic polymer.

In the present invention, the rubber-containing polymer (II) has an average particle size of less than 0.2 μm, preferably 0.02 μm.
5 to 0.18 μm. Such a rubber-containing polymer (I
I) is obtained, for example, by usual emulsion polymerization. When the average particle size is less than 0.2 μm, the transparency becomes good. The average particle size is more preferably 0.18 μm or less.
Further, from the viewpoint of film forming properties, the average particle size is 0.05.
It is preferably at least μm.

The thermoplastic polymer (III) used in the present invention
Is composed of 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another vinyl monomer copolymerizable therewith, and the reduced viscosity of the polymer (0.1 g of polymer is dissolved in 100 mL of chloroform). (Measured at 25 ° C.) exceeds 0.2 L / g.

In the present invention, the thermoplastic polymer (III)
The use of a compound improves the film-forming property, and is particularly useful when a high level of thickness accuracy and film-forming speed are required. In particular, the reduced viscosity of the thermoplastic polymer (III) is 0.1.
When the thickness exceeds 2 L / g, a film having good thickness accuracy can be obtained. This reduced viscosity is usually 0.1.
More than 2 L / g and 2 L / g or less, preferably 1.2 L / g
g or less.

Other vinyl monomers copolymerizable with methyl methacrylate, which are used as necessary for the thermoplastic polymer (III), include alkyl acrylates, alkyl methacrylates, and aromatic vinyl compounds. And vinyl cyanide compounds.

The thermoplastic polymer (III) is obtained by polymerizing these monomers. The polymerization method is preferably an emulsion polymerization method, and the polymer can be recovered in powder form by a usual emulsion polymerization method and a post-treatment method.

When the thermoplastic resin (III) is not used, the acrylic resin film of the present invention has a thermoplastic resin based on a total of 100 parts by mass of the thermoplastic polymer (I) and the rubber-containing polymer (II). It comprises 20 to 94.5 parts by mass of the polymer (I) and 5.5 to 80 parts by mass of the rubber-containing polymer (II) as main components.

When the thermoplastic polymer (III) is used, the thermoplastic polymer (I) and the rubber-containing polymer (II)
And 10 to 94.4 parts by mass of the thermoplastic polymer (I), 5.5 to 80 parts by mass of the rubber-containing polymer (II), and 100 parts by mass of the thermoplastic polymer (III). 0.1 to 10 parts by mass of a plastic polymer (III) as a main component. In this case, the thermoplastic polymer (II
When the amount of I) is at least 0.1 part by mass, the effect of improving film-forming properties is exhibited. On the other hand, when the amount is 10 parts by mass or less, the viscosity of the resin composition is suppressed, and the film-forming properties are reduced. It is possible to prevent a decrease and a decrease in transparency.

The amount of the elastic polymer (II-A) in the rubber-containing polymer (II) is 100 parts by mass in total of the component (I) and the component (II), or the component (I) and the component (I). 5 to 5 based on a total of 100 parts by mass of the component (II) and the component (III).
72 parts by mass. By setting the amount to 5 parts by mass or more, the whitening resistance to molding and the film forming property are improved. The lower limit is more preferably 18 parts by mass or more, particularly preferably 25 parts by mass or more. The upper limit is 72
By controlling the amount to be not more than part by mass, transparency and film forming property are improved.

The acrylic resin film of the present invention may contain, if necessary, a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact-resistant auxiliary, a foaming agent, a filler, a colorant, a gloss, and the like. An extinguisher, an ultraviolet absorber and the like can be included.

In particular, from the viewpoint of protecting the base material, it is preferable to add an ultraviolet absorber to impart weather resistance. The molecular weight of the ultraviolet absorber is preferably 300 or more, more preferably 400 or more. When an ultraviolet absorber having a molecular weight of 300 or more is used, mold contamination or the like due to volatilization of the ultraviolet absorber during vacuum molding or pressure molding in an injection molding die can be prevented. In general, a UV absorber having a higher molecular weight is less likely to cause long-term bleed-out after being processed into a film state, and UV absorbing performance is maintained for a longer period than a UV absorber having a lower molecular weight.

When the molecular weight of the ultraviolet absorbent is 300 or more, the amount of the ultraviolet absorbent volatilized before the acrylic resin film is extruded from the T-die and cooled by the cooling roll is small. Therefore, satisfactory performance is exhibited because the amount of the remaining ultraviolet absorber is sufficient. In addition, the volatile ultraviolet absorbent recrystallizes on the chain and the exhaust hood above the T-die, and grows with time, which eventually falls on the film and becomes a defect in appearance. The problem is also reduced.

The melting point of the ultraviolet absorbent is preferably 180 ° C. or lower, more preferably 150 ° C. or lower. When the melting point is 180 ° C. or less, it is difficult to bleed out the ultraviolet absorbent in a relatively short period of about several days to several months after processing into a film state. The relatively short-term bleed-out property is more likely to occur as the softness of the acrylic resin as the base material increases. In this case, if an ultraviolet absorber having a low melting point is used, such bleed-out property is less likely to occur.

As the ultraviolet absorbent, various conventionally known ultraviolet absorbents can be used. Commercially available benzotriazole ultraviolet absorbers having a molecular weight of 300 or more include, for example,
Ciba Geigy product names Tinuvin 234, Tinuvin 32
8, Tinuvin 329, trade name ADK STAB LA-31 of Asahi Denka Kogyo KK, and the like. Commercial products of the triazine-based ultraviolet absorber having a molecular weight of 300 or more include, for example, Tinuvin 1577 (trade name of Ciba-Geigy).

Commercially available benzotriazole-based ultraviolet absorbers having a melting point of 180 ° C. or lower include, for example, Tinuvin P, in addition to the above-mentioned Tinuvin 234, Tinuvin 328, and Tinuvin 329 of Ciba-Geigy. Examples of the triazine-based ultraviolet absorber having a melting point of 180 ° C. or less include, for example, the above-mentioned product name Tinuvin 1577 of Ciba-Geigy.
And the like.

Among these, Tinuvin 234, Tinuvin 328, Tinuvin 329, and Tinuvin 1577, which are ultraviolet absorbers having a molecular weight of 300 or more and a melting point of 180 ° C. or less, have a long-lasting ultraviolet-grade ability, and Is particularly preferred because of its excellent volatility resistance and bleed-out resistance for a relatively short period of time.

Examples of the method for producing the acrylic resin film of the present invention include various conventionally known film forming methods such as a melt casting method, a melt extrusion method such as a T-die method and an inflation method, and a calendar method. In terms of economy,
Particularly, the T-die method is preferable.

In the T-die method, it is preferable that the film cooled by the cooling roll is formed again so as to contact the cooling roll again. By doing so, the dirt generated on the cooling roll can be continuously removed, so that the cooling roll is always kept clean and the appearance of the film can be kept good. On the other hand, if the film is formed in such a manner that the film is brought into contact with the cooling roll only once, dirt accumulates on the cooling roll over time, and at a certain point, it is transferred to the film, resulting in a large appearance defect.

The acrylic resin film used as a substitute for coating is usually one which is printed by an appropriate printing method as needed in order to impart a design property to a molded product. In this case, it is preferable that the acrylic resin film is subjected to a one-sided printing process and used as a film having a pattern or the like printed on one side. In addition, it is preferable to dispose the printing surface on the lamination surface with the base resin at the time of molding, from the viewpoint of protection of the printing surface and imparting a sense of quality. Further, when using as a substitute for a transparent coating by making use of the color tone of a plastic or the like serving as a base material, the transparent coating can be used as it is. In particular, for applications that make use of the color tone of the base material, acrylic resin films are superior to vinyl chloride or polyester films in terms of transparency, depth, luxury and the like.

Further, the acrylic resin film of the present invention can be used after matting or coloring as required.

The thickness of the acrylic resin film is 300 μm.
m or less, more preferably 100 μm to 300 μm. When the thickness is 100 μm or more, a sufficient feeling of depth is obtained as the appearance of the molded product, and a sufficient thickness can be maintained even when the film is stretched particularly when molding into a complicated shape. In addition, the upper limit of these ranges is that the rigidity is appropriately suppressed to maintain good laminability and secondary workability, that the mass per unit area is kept economical, and that the film forming property is improved. It is significant in that the film is stably manufactured.

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

It is preferable that the acrylic resin film used in such a coating alternative use has, for example, a 60 ° surface gloss of 120% or more and a haze value of 2% or less at a thickness of 200 μm.

The acrylic laminated molded article of the present invention is characterized in that the acrylic resin film of the present invention is laminated on a substrate by fusion bonding or the like. Specifically, it is preferably obtained by subjecting an acrylic resin film to vacuum molding or air pressure molding in an injection mold, and then subjecting the resin as a base material to injection molding.

The resin constituting the base material is preferably one that can be melt-bonded to the acrylic resin film. For example, an ABS resin, an AS resin, a polystyrene resin, a polycarbonate resin, a vinyl chloride resin, an acrylic resin, a polyester resin, or various resins containing these as a main component are exemplified. From the viewpoint of adhesiveness, ABS resin, AS resin, polycarbonate resin, vinyl chloride resin or a resin containing these resins as a main component is preferable.
A resin, a polycarbonate resin or a resin containing these as a main component is more preferable. However, even a resin that does not melt and adhere, such as a polyolefin resin, can be used as a substrate. In this case, the acrylic resin film and the resin base material may be bonded at the time of molding by using a layer for bonding.

In order to obtain a two-dimensionally formed acrylic laminated product, an acrylic resin film may be laminated by a conventionally known lamination method such as thermal lamination. It is also possible to bond to a substrate that is not heat-sealed via an adhesive.

In order to obtain a three-dimensionally formed acrylic laminated molded product, it is sufficient to laminate-mold by a conventionally known molding method such as an insert molding method or an in-mold molding method. In particular, the in-mold molding method is preferable from the viewpoint of productivity.

In the in-mold molding method, after the acrylic resin film is heated, vacuum molding is performed in a mold having a vacuuming function. This method is excellent in workability and economical efficiency because film forming and injection molding can be performed in one step. The heating temperature is preferably equal to or higher than the temperature at which the acrylic resin film softens. Specifically, it depends on the thermal properties of the film or the shape of the molded product.
0 ° C. or higher. On the other hand, if the temperature is too high, the surface appearance tends to deteriorate and the releasability tends to deteriorate. This also depends on the thermal properties of the film or the shape of the molded product,
Usually, 170 ° C. or lower is preferable.

Further, from the viewpoint of energy efficiency, it is preferable that the preheating temperature during vacuum forming be lower. Specifically, the temperature is preferably 135 ° C. or lower. For a film that can be formed even when the preheating temperature is low, the preheating time can be shortened instead of lowering the preheating temperature. In this case, a high cycle of vacuum forming is possible, and the industrial use value is increased.

The acrylic resin film of the present invention has a relatively low required surface hardness and heat resistance level, and is very useful especially for applications such as injection molding where moldability is important. The acrylic resin film of the present invention has high elongation at high temperatures when a three-dimensional shape is imparted to the film by vacuum forming. For example, after giving a three-dimensional shape by this vacuum forming, the acrylic resin film and the base resin can be melt-integrated by injection molding.

[0061]

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 mass”, and “%” represents “% by mass”. Abbreviations in the examples are as follows. Methyl methacrylate MMA butyl acrylate BA allyl methacrylate AMA styrene St methyl acrylate MA t-butyl hydroperoxide tBH n-octyl mercaptan nOM.

Various physical properties of the thermoplastic polymers (I) and (III), the rubber-containing polymer (II), and the film were measured by the following test methods. 1) Reduced viscosity of the 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) Average particle diameter of rubber-containing polymer (II) The final particle diameter of the polymer latex of rubber-containing polymer (II) obtained by emulsion polymerization was measured using a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd. And was measured by a dynamic light scattering method. 3) Total light transmittance and haze of the film Evaluated according to JIS K6714. 4) Surface Gloss of Film The surface gloss at 60 ° was measured using a gloss meter (Model GM-26D, manufactured by Murakami Color Research Laboratory). 5) Film-forming properties Films with a thickness of 100 μm were formed by the T-die method. Films that could be formed without cutting the film for 5 hours or more were marked “O”, and the film was cut several times in 5 hours. The sample in which no sample was obtained due to the cutting of the film was indicated by “△”, and the sample in which no sample was obtained due to cutting of the film was indicated by “×”. 6) Moldability "○" indicates that no whitened portion remains in the molded product at the corner when vacuum forming was performed under preheating conditions of 125/130/135/140 ° C * 1 minute, “×” was assigned. 7) Volatility resistance of ultraviolet absorber When the film forming operation of the film was performed for 5 hours, the exhaust hood was installed at a position about 50 cm above the T-die.
The generation of crystals of the volatilized ultraviolet absorber was observed. The case where no crystal was precipitated was indicated by “「 ”, and the case where there was no crystal was indicated by“ × ”. 8) Bleed-out resistance of the ultraviolet absorber for a relatively short period of time The obtained film was placed in an atmosphere at 70 ° C for 5 days, and the state of the film surface after 5 days was observed. ○ ”, and the case where the surface became white and the ultraviolet absorbent bleed out was marked“ × ”.

Example 1 a) Production of Rubber-Containing Polymer (II) -a The following (a) was charged into a reaction vessel, and the following raw materials were stirred at 80 ° C. for 200 minutes under a nitrogen atmosphere while stirring. (B) (Raw material for polymer (II-A)) was continuously added, followed by polymerization for further 120 minutes to obtain a latex of elastic polymer (II-A).

To the latex of the elastic polymer (II-A), the following (C) was subsequently added, and the mixture was stirred at 80 ° C. under a nitrogen atmosphere at 80 ° C. with stirring to obtain the following raw material (D).
(Raw material for rubber polymer (II-B)) is continuously added over 100 minutes, and then the polymerization is further carried out continuously at 80 ° C. for 60 minutes to form a hard polymer (II-B). A latex of the contained polymer (II) -a was obtained. The average particle diameter of the rubber-containing polymer (II) -a was 0.12 μm.

The latex of the rubber-containing polymer (II) -a was subjected to coagulation, coagulation and solidification using calcium acetate, followed by filtration, washing with water and drying, followed by drying.
I) -a was obtained.

(A) 310 parts of deionized water Partially neutralized product of a mixture of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonyl phenyl ether) phosphoric acid sodium hydroxide 0.5 parts Sodium carbonate 0.1 parts Sodium formaldehyde sulfoxylate 0.5 parts Ferrous sulfate 0.00024 parts Disodium ethylenediaminetetraacetate 0.000072 parts (b) BA 81.0 parts St 19.0 parts AMA 1.0 part tBH 0.25 parts Partially neutralized product of a mixture of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonyl phenyl ether) phosphoric acid sodium hydroxide 1.1 Part (c) deionized water 10 parts sodium formaldehyde sulfoxylate 0.15 part (d) M MA 57.0 parts MA 3.0 parts nOM 0.2 parts tBH 0.1 parts.

B) Production of thermoplastic polymer (III) Into a reaction vessel were charged 200 parts of ion-exchanged water purged with nitrogen, and 1 part of an emulsifier, potassium oleate, and 0.3 part of potassium persulfate. Next, 40 copies of MMA, BA10
Parts, 0.005 part of nOM, 65 ° C under nitrogen atmosphere
For 3 hours to complete the polymerization. Subsequently, M
A monomer mixture consisting of 48 parts of MA 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, thereby obtaining a latex of a thermoplastic polymer (III). This latex was added to a 0.25% aqueous sulfuric acid solution to coagulate the polymer, followed by dehydration, washing with water, and drying to recover a powdery thermoplastic polymer (III). The reduced viscosity ηsp / c of this thermoplastic polymer (III) was 0.38 L / g.

C) Production of Acrylic Resin Film The rubber-containing polymer (II) -a and the thermoplastic polymer (III) obtained as described above and the MMA / MA copolymer as the thermoplastic polymer (I) The mixture (MMA / MA = 98/2, reduced viscosity 0.06 L / g) was mixed at a ratio shown in Table 1 using a Henschel mixer. Then, using a 40 mmφ twin screw type extruder (L / D = 26), the mixture is melt-kneaded at a cylinder temperature of 200 ° C. to 260 ° C. and a die temperature of 250 ° C., and is pelletized. Obtained.

The pellet was dried at 80 ° C. for 24 hours,
Using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 00 mm T die, cylinder temperature 200 ° C. to 240 ° C., T die temperature 250 ° C.
A film having a thickness of 00 μm was formed.

The obtained acrylic resin film was printed and evaluated for vacuum moldability using a mold having a vacuuming function.
Then, with the formed film arranged in the mold,
ABS resin (trade name: Diapet ABS Bulk Sum TM20, manufactured by Mitsubishi Rayon Co., Ltd.) is injection-molded on the printing surface side,
An acrylic laminated molded product was obtained.

As described above, the film forming property was 100 μm.
A film having a thickness of m was formed. Table 1 shows the film forming properties of the obtained films, and Table 2 shows the evaluation results of the physical properties and moldability of the films.

<Examples 2, 3, and 4> The amounts of the thermoplastic polymer (I), the rubber-containing polymer (II) -a, and the thermoplastic polymer (III) were changed as shown in Table 1. Except for preparing film compositions 2, 3, and 4 in the same manner as in Example 1, and producing an acrylic resin film and an acrylic laminated molded article in the same manner as in Example 1 except that these were used.
evaluated.

Example 5 In the polymerization of the rubber-containing polymer (II) -a of Example 1, the average particle size was 0.09 μm.
The rubber-containing polymer (II) -b was obtained by changing the amount of the emulsifier and the like in (A) and (B). The average particle size is 0.09
A film composition 5 was prepared in the same manner as in Example 1 except that each compounding amount was as shown in Table 1 using a rubber-containing polymer (II) -b of μm, and this composition was used. Except for the above, an acrylic resin film and an acrylic laminated molded product were manufactured and evaluated in the same manner as in Example 1.

Example 6 In the polymerization of the rubber-containing polymer (II) -a of Example 1, the average particle size was 0.18 μm.
The rubber-containing polymer (II) -c was obtained by changing the amount of the emulsifier of the raw materials (a) and (b) so that This average particle size is 0.
A film composition 6 was prepared in the same manner as in Example 1 except that the rubber-containing polymer (II) -c of 18 μm was used and the compounding amounts were as shown in Table 1, and this composition was used. Except for the above, an acrylic resin film and an acrylic laminated molded product were manufactured and evaluated in the same manner as in Example 1.

<Example 7> An acrylic resin film and an acrylic laminate were prepared in the same manner as in Example 2 except that the substrate to be injection-molded was changed to a polycarbonate resin (trade name: Iupilon S100, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Molded articles were manufactured and evaluated.

<Example 8> Instead of the rubber-containing polymer (II) -a of Example 2, a multilayer-structured polymer 1 (rubber-containing polymer (R) was prepared in accordance with the examples of JP-A-7-149994. II) -d, an elastic polymer (II-A) containing two layers of butyl acrylate and having an average particle diameter of 0.09 μm and 2
Layered Hard Polymer Containing Methyl Methacrylate (II-
Except that the film composition 7 was prepared in the same manner as in Example 1 except that each compounding amount was as shown in Table 1 using the multilayer structure polymer 1) comprising B), and that this composition was used. In the same manner as in Example 1, an acrylic resin film and an acrylic laminated molded product were manufactured and evaluated.

Example 9 A film composition was prepared in the same manner as in Example 8, except that the amounts of the thermoplastic polymer (I) and the rubber-containing polymer (II) -d were changed as shown in Table 1. Example 8 except that Preparation 8 was used and this composition was used.
In the same manner as in the above, an acrylic resin film and an acrylic laminated molded product were manufactured and evaluated.

<Example 10> The thermoplastic polymer (I) was
A film composition 9 was prepared in the same manner as in Example 8 except that the MMA / MA copolymer (MMA / MA = 90/10, reduced viscosity 0.06 L / g) was used. An acrylic resin film and an acrylic laminated molded product were manufactured and evaluated in the same manner as in Example 8 except for the fact that they were not present.

<Example 11> 56 parts of the rubber-containing polymer (II) -a obtained in Example 1 and 2 parts of the thermoplastic polymer (III) were used.
Parts, MMA / MA copolymer as thermoplastic polymer (I) (MMA / MA = 90/10, reduced viscosity 0.06 L /
A film composition 12-A was prepared in the same manner as in Example 1 except that 42 parts of g) and 3 parts of Ciba Geigy's Tinuvin 234 as an ultraviolet absorber were mixed using a Henschel mixer. An acrylic resin film and an acrylic laminated molded product were manufactured and evaluated in the same manner as in Example 1 except that this composition 12-A was used. In addition, the resistance to volatilization of the ultraviolet absorbent during film formation was good, and the bleed-out resistance of the ultraviolet absorbent in the obtained film was good.

<Example 12> An acrylic resin film was prepared in the same manner as in Example 11 except that a film composition 12-B prepared by using 3 parts of tinuvin 329 instead of tinuvin 234 was used. An acrylic laminated molded product was manufactured and evaluated. In addition, the resistance to volatilization of the ultraviolet absorbent during film formation was good, and the bleed-out resistance of the ultraviolet absorbent in the obtained film was good.

Example 13 Example 11 was the same as Example 11 except that the film composition 12-C prepared using 3 parts of tinuvin P instead of tinuvin 234 was used.
In the same manner as in the above, an acrylic resin film and an acrylic laminated molded product were manufactured and evaluated. In addition, the resistance to volatilization of the ultraviolet absorbent during film formation was ×, and the bleed-out resistance of the ultraviolet absorbent in the obtained film was ○.

<Embodiment 14> In place of Tinuvin 234 in Embodiment 11, Adekastab LA3 manufactured by Asahi Denka Kogyo KK
An acrylic resin film and an acrylic laminated molded product were manufactured and evaluated in the same manner as in Example 11, except that the film composition 12-D prepared using 3 parts of No. 1 was used. The resistance to volatilization of the ultraviolet absorber during film formation was ○, and the resistance to bleed-out of the ultraviolet absorber in the obtained film was ×.

<Comparative Examples 1 and 2> Thermoplastic polymer (I),
Example 1 except that the compounding amounts of the rubber-containing polymer (II) -a and the thermoplastic polymer (III) were changed as shown in Table 1.
An attempt was made to form a film in the same manner as described above, but no sample was obtained due to the cutting of the film.

Comparative Examples 3 and 4 Instead of the rubber-containing polymer (II) -a of Example 1, the rubber-containing polymer (rubber-containing polymer) obtained according to Example 1 of JP-A-8-323934 was used. (II) -e, a rubber-containing polymer composed of an elastic polymer containing butyl acrylate (II-A) and a hard polymer containing methyl methacrylate (II-B) having an average particle diameter of 0.29 μm. A film composition 10, 11 was prepared in the same manner as in Example 1 except that the blending amounts were as shown in Table 1, and an acrylic resin film was prepared in the same manner as in Example 1 except that these were used. An acrylic laminated molded product was manufactured and evaluated.

[0085]

[Table 1]

[0086]

[Table 2]

<Evaluation> From the evaluation of the examples and comparative examples,
The following has been found. . Each of the films of Examples 1 to 14 has good film-forming properties, transparency, and molding whitening resistance. . Since the content of the rubber-containing polymer (II) and the elastic polymer (II-A) is small in the film of Comparative Example 1, the film-forming properties of the film are poor. . The film of Comparative Example 2 has a large content of the rubber-containing polymer (II), so that the film-forming property of the film is poor. . Although the film of Comparative Example 3 had good transparency, the average particle diameter of the rubber-containing polymer (II) was large.
Poor moldability, limits the applications used, and has low industrial value. . Although the film of Comparative Example 4 has relatively good moldability, the average particle diameter of the rubber-containing polymer (II) is large, so the transparency is poor, and the use of the film is restricted. Low utility value.

[0088]

As described above, according to the present invention,
It is possible to obtain an acrylic resin film as a substitute for painting and an acrylic laminated molded product having excellent transparency and whitening resistance to molding, particularly suitable for in-mold molding.

Continued on the front page F term (reference) 4F071 AA33 AA33X AA76 AA77 AA88 AF32 BA01 BB06 BC01 BC12 4F206 AA21E AA45 AF16 AG03 JA07 JB13 JB19 4J002 BG05W BG06W BN12X EU176 FD056

Claims (7)

[Claims] 1. A thermoplastic polymer (I) 2 shown below
0 to 94.5 parts by mass and 5.5 to 5.5 parts of the rubber-containing polymer (II).
80 parts by mass, and the amount of the elastic polymer (II-A) in the rubber-containing polymer (II) is 5 to 72 parts by mass [component (I)
And a total of 100 parts by mass of the component (II)]. Thermoplastic polymer (I) alkyl methacrylate 50 to 100% by mass;
It is composed of 0 to 50% by mass of an alkyl acrylate and 0 to 49% by mass of another vinyl monomer copolymerizable therewith. The reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 mL of chloroform, 0.1 L / g at 25 ° C)
The following thermoplastic polymers. Rubber-Containing Polymer (II) In the presence of an elastic polymer (II-A) having one or more layers, which is an inner layer obtained by polymerizing a monomer containing an alkyl acrylate, methacrylic acid Average particle size having a multilayer structure of two or more layers obtained by graft-polymerizing a monomer containing an alkyl ester to form a hard polymer (II-B) having one or two or more layers as an outer layer Rubber-containing polymer of less than 0.2 μm. 2. A thermoplastic polymer (I) 1 shown below
0 to 94.4 parts by mass, rubber-containing polymer (II) 5.5 to 80
And 0.1 to 10 parts by mass of the thermoplastic polymer (III), and the amount of the elastic polymer (II-A) in the rubber-containing polymer (II) is 5 to 72 parts by mass [component ( I), component (II) and component (III) in total of 100 parts by mass]. Thermoplastic polymer (I) alkyl methacrylate 50 to 100% by mass;
It is composed of 0 to 50% by mass of an alkyl acrylate and 0 to 49% by mass of another vinyl monomer copolymerizable therewith. The reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 mL of chloroform, 0.1 L / g at 25 ° C)
The following thermoplastic polymers. Rubber-Containing Polymer (II) In the presence of an elastic polymer (II-A) having one or more layers, which is an inner layer obtained by polymerizing a monomer containing an alkyl acrylate, methacrylic acid A hard polymer having a structure of one or two or more layers as an outer layer by graft-polymerizing a monomer mainly containing an alkyl ester (II-
A rubber-containing polymer having a multilayer structure of two or more layers and having an average particle diameter of less than 0.2 μm, which is obtained by forming B). A thermoplastic polymer (III) comprising 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another vinyl monomer copolymerizable therewith;
Reduced viscosity of polymer (0.1 g of polymer
A thermoplastic polymer having a solubility in 0 mL and measured at 25 ° C.) of more than 0.2 L / g. 3. The acrylic resin film as a substitute for coating according to claim 1, wherein at a thickness of 200 μm, the surface glossiness at 60 ° is 120% or more and the haze value is 2% or less. 4. The acrylic resin film according to claim 1, wherein a picture is printed on one side. 5. An acrylic laminated molded product obtained by laminating the acrylic resin film according to claim 1 on a substrate. 6. The acrylic resin film according to claim 1, which is obtained by subjecting the acrylic resin film according to claim 1 or 2 to vacuum molding or pressure molding in an injection molding die, and then subjecting the resin as a base material to injection molding. Acrylic laminated molded product. 7. A compound having a molecular weight of 300 or more and a melting point of 180.
The acrylic resin film as a substitute for coating according to claim 1, wherein the acrylic resin film contains 0.1 to 5% by weight of an ultraviolet absorber having a temperature of not more than 0C.