JP2002080679A - 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 of which the moldability and the resistance to plasticizer-caused whitening are compatible with each other without detriment to surface hardness and heat resistance; and an acrylic laminate molding. SOLUTION: This acrylic resin film comprises (I) 75-94.5 pts. thermoplastic polymer containing 50-100% MMA units and having a reduced viscosity of 0.1 L/g or lower and (II) 5.5-25 pts. rubber-containing polymer having an average particle size of 0.2-0.4 μm and a three-layer structure consisting of (II-A) an intermediate MMA+MA polymer layer having a Tg of 0 deg.C or higher but lower than 25 deg.C, (II-B) an intermediate rubber polymer layer having a Tg lower than 0 deg.C, and (II-C) an outermost MMA polymer layer, provided the sum of polymer (I) and polymer (II) is 100 pts. and that the sum of polymer (II-A) and polymer (II-B) is 5-18 pts. 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 laminated molded product obtained by laminating an acrylic resin film as a substitute for a specific coating,
And an acrylic resin film as a substitute for painting used in the production of such molded articles.

[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, Injection molding of 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 suitable for in-mold molding are disclosed in JP-A-8-323934, JP-A-11-147237, 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.

Further, Japanese Patent Application Laid-Open Nos. 2000-167869, 2000-178365 and 20
Patent Document 00-178399 discloses an acrylic resin film which can be used for in-mold molding using a rubber elastic body having a polymer having a glass transition temperature of 20 ° C. or more inside a rubber layer.

[0005]

In recent years, members having an acrylic resin film layer as a surface layer formed by an in-mold molding method have been used for automobile interiors.

For example, JP-A-8-323934 discloses that an acrylic resin film having excellent surface hardness, heat resistance and moldability can be obtained by using a smaller amount of a rubber-containing polymer having a specific particle size than before. Has been described. However, when a suction cup made of polyvinyl chloride or the like containing a plasticizer such as DOP (dioctyl phthalate) is attached to a member on which the film is laminated, there is a problem that whitening occurs due to aging.

[0007] For example, Japanese Patent Application Laid-Open No. H11-147237 proposes to use a rubber-containing polymer having a hard core structure having a glass transition temperature of about 105 ° C. According to this method, although an acrylic resin film having excellent surface hardness can be obtained, there is a problem that the moldability is inferior because the elastic modulus is higher than that of the soft core rubber. Specifically, because the film is hard, the trim end face during film formation becomes unstable, the preheating time during vacuum forming becomes longer and productivity decreases, whitening occurs at corners, There is a problem that the film following ability of the part to the mold is deteriorated, and the film is broken when the part is removed from the mold.

Further, Japanese Patent Application Laid-Open Nos. 2000-167869, 2000-178365 and 20
The acrylic resin film described in JP-A-00-178399 has a glass transition temperature of 20 ° C. inside the rubber layer.
A rubber elastic body having the above polymer is used. However, substantially, as in the case of the rubber-containing polymer described in JP-A-11-147237, the glass transition temperature is about 10%.
Since it relates to a rubber elastic body having a hard core structure having an innermost polymer at 5 ° C., it has the same problem as the technique described in JP-A-11-147237.

[0009] An object of the present invention is to solve these problems of the prior art. Specifically, the present invention has been developed for use as a substitute for coating in which the plasticizer whitening resistance and moldability are both compatible without impairing the surface hardness and heat resistance. An object of the present invention is to provide an acrylic resin film and an acrylic laminated molded product using the same.

[0010]

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, a rubber-containing polymer having a specific structure and a specific thermoplastic polymer have been identified. The present inventors have found that an acrylic resin film containing the same in a ratio has a very excellent effect, and have completed the present invention.

That is, the present invention comprises 75 to 94.5 parts by mass of a thermoplastic polymer (I) and 5.5 to 25 parts by mass of a rubber-containing polymer (II) shown below. The elastic polymer ((II-A) + (II-A) comprising the innermost layer polymer (II-A) and the rubber polymer (II-B) in (II)
-B)) is 5 to 18 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) The innermost layer polymer having a glass transition temperature of 0 ° C or higher and lower than 25 ° C obtained by polymerizing a monomer containing an alkyl methacrylate and an alkyl acrylate as the innermost layer (II- A) wherein the intermediate layer has a glass transition temperature of 0 obtained by polymerizing a monomer containing an alkyl acrylate.
The outermost layer is composed of a rubber polymer (II-B) having a temperature lower than 0 ° C., and the outermost layer is composed of an outermost layer polymer (II-C) obtained by polymerizing a monomer containing an alkyl methacrylate. A rubber-containing polymer having an average particle size of 0.2 to 0.4 μm.

Further, the present invention relates to a thermoplastic polymer (I) of 65 to 94.4 parts by mass and the rubber-containing polymer (I).
I) 5.5 to 25 parts by mass of the thermoplastic polymer (III) shown below and 0.1 to 10 parts by mass of the innermost polymer (II-) in the rubber-containing polymer (II). A) and an elastic polymer ((II-A) +) comprising a rubber polymer (II-B)
(II-B)) in an amount of 5 to 18 parts by mass [total 100 parts by mass of component (I), component (II) and component (III)]. . 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.

[0014]

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.

The alkyl methacrylate used for the thermoplastic polymer (I) includes 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, butyl acrylate and the like. The alkyl acrylate is used in the range of 0 to 50% by mass, preferably 0.1 to 40% by mass.

As the other copolymerizable vinyl monomer 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:
A graft copolymer having a three-layer structure containing an alkyl acrylate as a main component of a rubber, which is an important component for achieving both plasticizer whitening resistance and moldability.

Specifically, in the rubber-containing polymer (II), the innermost layer has a glass transition temperature obtained by polymerizing a monomer containing an alkyl methacrylate and an alkyl acrylate having a glass transition temperature of 0 ° C. to 25 ° C. Less than the innermost layer polymer (II
-A), wherein the intermediate layer comprises a rubber polymer (II-B) having a glass transition temperature of less than 0 ° C obtained by polymerizing a monomer containing an alkyl acrylate, and the outermost layer comprises methacrylic acid. An outermost layer polymer (II-C) obtained by polymerizing a monomer containing an acid alkyl ester, is a rubber-containing polymer having a three-layer structure and an average particle diameter of 0.2 to 0.4 μm.

The rubber-containing polymer (II-A) is obtained from a monomer containing an alkyl methacrylate and an alkyl acrylate as main components. As the alkyl acrylate, various conventionally known alkyl acrylates can be used. Things can be used. Particularly, butyl acrylate, 2-ethylhexyl acrylate and the like are preferable. Similarly, various conventionally known alkyl methacrylates can be used, but methyl methacrylate and butyl methacrylate are particularly preferable. Rubber polymer (II-B)
The same applies to the alkyl acrylate used as the main component of the acrylate and the alkyl methacrylate used as the main component of the outermost layer polymer (II-C).

The elastic polymer ((II-A) + (II-) comprising the innermost layer polymer (II-A) and the rubber polymer (II-B)
In obtaining B)), a vinyl monomer other than the alkyl acrylate and the alkyl methacrylate can be copolymerized. As the vinyl monomer, styrene, acrylonitrile and the like are preferable.

In order to obtain an elastic polymer ((II-A) + (II-B)), a copolymerizable crosslinkable monomer is usually used. The crosslinking 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 use of the copolymerizable crosslinkable monomer is preferable because whitening caused by swelling of the rubber due to the plasticizer contained in the resin in contact with the film can be reduced.

Elastic polymer ((II-A) + (II-B))
The ratio of the innermost layer polymer (II-A) is 20 to 60% by mass and the rubber polymer (II-B) is 80 to 40% by mass.
It is preferable from the viewpoint of plasticizer whitening resistance and moldability. In particular, the content of the innermost layer polymer (II-A) is more preferably 30% by mass or more. From the viewpoint of moldability, it is more preferable that the ratio of the rubber polymer (II-B) is 50% by mass or more.

The innermost layer polymer (II-A) is necessary for the film to exhibit the plasticizer whitening resistance. The glass transition temperature of the innermost layer polymer (II-A) is 0 ° C. or more and 25 ° C.
Is less than. If the glass transition temperature is less than 0 ° C., the plasticizer whitening resistance of the film is inferior, and if it exceeds 25 ° C., the moldability during vacuum forming of the film is inferior. From the viewpoint of plasticizer whitening resistance, the glass transition temperature of the innermost layer polymer (II-A) is preferably 2 ° C. or higher, more preferably 15 ° C. or higher. On the other hand, from the viewpoint of moldability during vacuum forming, the glass transition temperature of the innermost layer polymer (II-A) is preferably 24 ° C or lower, more preferably 10 ° C or lower. In consideration of the balance between the plasticizer whitening resistance and the moldability of the film, the glass transition temperature of the innermost layer polymer (II-A) is preferably 2 ° C. or more and less than 25 ° C.
The temperature is more preferably from 24 ° C to 24 ° C.

The outermost polymer (II-C) is obtained by graft-polymerizing a monomer mainly composed of an alkyl methacrylate in the presence of an elastic polymer ((II-A) + (II-B)). Can be formed. The amount of the alkyl methacrylate used is preferably 50% by mass or more in the monomers used for the outermost layer polymer (II-C). Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid 2
-Ethylhexyl, cyclohexyl methacrylate and the like.

In obtaining the outermost layer polymer (II-C), another vinyl monomer copolymerizable with the alkyl methacrylate can be used in combination. Examples of other vinyl monomers include, but are not limited to, methyl acrylate, butyl acrylate, alkyl acrylates such as cyclohexyl acrylate, styrene, acrylonitrile, and the like. The amount of the other vinyl monomer used is preferably 50% by mass or less in the monomer used for the outermost layer polymer (II-C).

The outermost layer polymer (II-C) was added to 10 parts by mass of the elastic polymer ((II-A) + (II-B)).
The amount is preferably from 400 to 400 parts by mass, more preferably from 20 to 200 parts by mass. The lower limit of these ranges is significant in that aggregation of the elastic polymer hardly occurs and transparency is improved. In addition, the outermost layer polymer (II-
The polymerization for obtaining C) can be performed in at least one stage.

In the present invention, the rubber-containing polymer (II) has an average particle size of 0.2 to 0.4 μm. When the average particle size is less than 0.2 μm, the rubber-containing polymer (I
With the use amount of (I), the obtained film becomes brittle, and the film forming property becomes poor. In addition, the average particle diameter is 0.4 μm
If it exceeds, the transparency of the film becomes poor. In particular, the average particle diameter is preferably 0.25 to 0.35 μm in consideration of the transparency and film forming property of the film.

The rubber-containing polymer (II) can be produced by conventionally known emulsion polymerization or the like. The polymerization temperature at that time,
Depending on the type and amount of the polymerization initiator used,
120 ° C, preferably 60 to 95 ° C.

As the polymerization initiator, various conventionally known ones can be used. As a method of adding it, a method of adding to one or both of the aqueous phase and the monomer phase can be used.

As the emulsifier, anionic, cationic and nonionic surfactants can be used. In particular, an anionic surfactant is preferable. Examples of anionic surfactants include carboxylate salts such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate, sulfates such as sodium lauryl sulfate, and dioctyl sulfosuccinate. Sulfonates such as sodium silicate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, and phosphate salts such as sodium polyoxyethylene alkylphenyl ether phosphate.

Various conventionally known coagulation methods such as an acid coagulation method, a salt coagulation method, a freeze coagulation method and a spray drying method can be used for the polymer latex obtained by the emulsion polymerization method. As the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid can be used. As the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate, and calcium chloride can be used. And organic salts such as calcium acetate and magnesium acetate. The rubber-containing polymer (II) can be obtained by further washing, dehydrating and drying the coagulated polymer.

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 a polymer latex produced by a conventionally known emulsion polymerization method is separated and recovered by various coagulants, or a solid content is separated and recovered by spray drying to obtain a polymer powder. Obtained by obtaining.

When the thermoplastic polymer (III) is not used, the acrylic resin film of the present invention has a thermoplastic resin based on 100 parts by mass of the total of the thermoplastic polymer (I) and the rubber-containing polymer (II). It comprises 75 to 94.5 parts by mass of the polymer (I) and 5.5 to 25 parts by mass of the rubber-containing polymer (II) as main components.

The thermoplastic polymer (III) is obtained by polymerizing these monomers. The polymerization method is preferably an emulsion polymerization method, and a polymer latex produced by a conventionally known emulsion polymerization method is separated and recovered by various coagulants, or a solid content is separated and recovered by spray drying to obtain a polymer powder. Obtained by obtaining.

When the thermoplastic polymer (III) is not used, the acrylic resin film of the present invention has a thermoplastic resin based on 100 parts by mass of the total of the thermoplastic polymer (I) and the rubber-containing polymer (II). It comprises 75 to 94.5 parts by mass of the polymer (I) and 5.5 to 25 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 65 to 94.4 parts by mass of the thermoplastic polymer (I), 5.5 to 25 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) + (II-B)) in the rubber-containing polymer (II) is 100 parts by mass in total of the components (I) and (II), or The amount is 5 to 18 parts by mass, preferably 8 to 12 parts by mass, based on 100 parts by mass in total of component (I), component (II) and component (III). By setting the amount to 5 parts by mass or more, the film is less likely to be brittle, and the film forming property is improved. Further, when the content is 18 parts by mass or less, the transparency of the film is improved, and the surface hardness required for the coating substitute film is obtained.

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 substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. The molecular weight of the UV absorber is 3
00 or more is preferable, and 400 or more is more preferable. 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. 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. The former commercial product is Ciba Geigy's trade name Tinuvin 234, the Asahi Denka Kogyo's trade name Adecastab LA-31, and the latter commercial product is Ciba Geigy's trade name Tinuvin 1577.
Etc.

The heat distortion temperature (measured based on ASTM D648) of the acrylic resin film of the present invention is preferably 80 ° C. or higher. When the heat deformation temperature is 80 ° C. or higher, surface roughness due to residual stress is less likely to occur during heating of the acrylic laminated molded product. Further, when used for vehicle applications, if the heat deformation temperature is 100 ° C. or more, it can be used, for example, near the handle portion, and if it is 110 ° C. or more, it can be used, for example, near the meter panel portion. Therefore, the industrial use value is increased.

The thermal deformation temperature of the acrylic resin film of the present invention depends on the amount of the rubber-containing polymer (II) used, but is mainly determined by the thermal deformation temperature of the thermoplastic polymer (I). The heat distortion temperature of the thermoplastic polymer (I) can be adjusted by adjusting the monomer composition of the thermoplastic polymer (I) by a conventionally known method. Although it depends on various conditions, for example, when methyl acrylate is used as a polymerization component, the content of methyl methacrylate in the thermoplastic polymer (I) is set to 88% by mass or more in order to set the heat distortion temperature to 80 ° C. or more. The heat distortion temperature can be adjusted to 100 ° C. or more by adjusting the methyl methacrylate content in the thermoplastic polymer (I) to 95% by mass or more. In order to set the heat deformation temperature to 110 ° C. or higher, maleimides such as maleic anhydride and phenylmaleimide are copolymerized in the thermoplastic polymer (I). Of course, even when the heat distortion temperature is 80 ° C. or more or 100 ° C. or more, it is also possible to copolymerize maleimides such as maleic anhydride and phenylmaleimide, thereby reducing the content of methyl methacrylate.

Examples of the method for producing the acrylic resin film of the present invention include various 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.

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 not particularly limited, but is preferably 300 μm or less, and
300 μm is more preferred. When the thickness is 100 μm or more, a sufficient feeling of depth is obtained as the appearance of a molded product, and a sufficient thickness is obtained even when the film is stretched, particularly when it is molded 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, the mass per unit area is kept economical, and the film forming property is stable. It is significant in the point of producing a film.

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.

The acrylic resin film used for the above-mentioned substitute for painting is, for example, a pencil hardness (JIS K5400).
Is preferably H or more.

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 fuse, such as a polyolefin resin, can be used as a base material. 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.

As described above, a film is formed by vacuum forming.
When providing a three-dimensional shape, whitening of the corners of the mold and followability to the corners are important, and this is a processing method that makes the most of the characteristics of the acrylic resin film for coating substitution of the present invention. That is, the acrylic resin film of the present invention has high elongation at high temperatures, and is very advantageous in such a case. In addition, according to the in-mold molding method, the acrylic resin film and the base resin are melted and integrated by injection molding after the film is formed into a three-dimensional shape by vacuum molding, thereby forming the acrylic resin film layer on the surface layer. Can be obtained.

The industrial application of the acrylic laminated molded article of the present invention is not particularly limited. For example, automobile interior parts such as console boxes and shift lever boxes, vehicle exterior parts such as motorcycle cowlings, home appliances, furniture, It can also be used for members that have been painted conventionally, such as building materials,
It is very useful in these applications.

[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 Methyl acrylate MA butyl acrylate BA Styrene St Allyl methacrylate AMA 1,3-butylene glycol dimethacrylate 1,3BD t-butyl hydroperoxide tBH t-hexyl hydroperoxide tHH n-octyl mercaptan nOM.

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) Glass transition temperature of polymer DSC (DSC200 manufactured by Seiko Instruments Inc.)
Was measured using the obtained powder of the rubber-containing polymer (II) to determine the glass transition temperature of the innermost layer polymer (II-A) and the rubber polymer (II-B). . However, the glass transition temperature of the polymer in the rubber-containing polymers (II) -b and (II) -c used in Comparative Examples was determined by salting out the latex at the time when the polymerization was completed. The measurement was carried out. 4) Total light transmittance and haze of the film Evaluated according to JIS K6714. 5) Surface gloss of film The surface gloss at 60 ° was measured using a gloss meter (Model GM-26D manufactured by Murakami Color Research Laboratory). 6) Pencil hardness of molded article Evaluated according to JIS K5400. 7) Film-forming properties Films with a thickness of 100 μm were formed by the T-die method. Films that could be formed without breaking the film for 5 hours or more were evaluated as “O”. Those that occurred were evaluated as “Δ”, and those that did not produce any sample due to film cutting were evaluated as “x”. 8) Thermal deformation temperature of film composition A pellet of the film composition is subjected to ASTM by injection molding.
Formed into a heat deformation temperature measurement specimen based on D648, 80 ° C
After annealing for 24 hours at low load (0.45 MPa)
Measured according to STM D648. 9) Plasticizer whitening resistance A soft vinyl chloride resin sucker using DOP as a plasticizer was adhered for one month in a 20 ° C atmosphere, and the degree of whitening was observed. Those with slight whitening were rated "△", and those with whitening were rated "x". 10) Moldability-Film whitening at corners The whitening of the corners when vacuum forming was performed was evaluated, and those without whitening were evaluated as "」 ". When the whitening remained very little, it was evaluated as "△", and when whitening remained without disappearing, it was evaluated as "x".・ Correspondence of film at corners The moldability of the corners when performing in-mold molding was evaluated. If there was no particular problem, "○" was indicated, and there were slight corners that were not in contact with the mold during vacuum molding. However, "△" indicates that the injection molding was completed without any problem, and "x" indicates that there was a part that did not touch the mold at the corner during vacuum molding and the film was sometimes torn when injection molded. .

<Example 1> a) Production of rubber-containing polymer (II) -a Under a nitrogen atmosphere, deionized water 2 was placed in a reaction vessel equipped with a reflux condenser.
44 parts were added, the temperature was raised to 80 ° C., the following (a) was added, and while stirring, 1/15 of the mixture of the following raw materials (b) (raw materials of the polymer (II-A)) was added. 15
Minutes. Thereafter, the remaining raw material (b) was continuously added at an increase rate of the monomer mixture to water of 8% / hour. Thereafter, the mixture was kept for 1 hour to obtain a latex of the polymer (II-A).

Subsequently, 0.6 part of sodium formaldehyde sulfoxylate was added to this latex, and the mixture was kept for 15 minutes and stirred at 80 ° C. under a nitrogen atmosphere to obtain the following raw material (c) (rubber polymer ( II-B)) was added continuously at an increasing rate of 4% / hour of the monomer mixture with respect to water. Thereafter, the mixture is held for 2 hours to polymerize the rubber polymer (II-B), whereby the elastic polymer ((II-A) +
A latex of (II-B)) was obtained.

Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the latex, and
The raw material (d) (raw material of the outermost layer polymer (II-C)) shown below is stirred at 80 ° C. under a nitrogen atmosphere while keeping the mixture at a rate of 10% / hour for a monomer mixture with respect to water. Was added continuously. Then, by holding for 1 hour, the outermost layer polymer (II-C) is performed to obtain the rubber-containing polymer (II).
-A latex was obtained. The average particle size of the rubber-containing polymer (II) -a was 0.28 μm.

The latex of the rubber-containing polymer (II) -a was subjected to coagulation, aggregation and solidification using calcium acetate, followed by filtration, washing with water and drying, followed by drying.
I) -a was obtained. (A) Sodium formaldehyde sulfoxylate 0.6 part Ferrous sulfate 0.00012 parts Disodium ethylenediaminetetraacetate 0.0003 part (b) MMA 22.0 parts BA 15.0 parts St 3.0 parts AMA 0 0.4 part 1.3BD 0.14 part tBH 0.18 part Part of a mixture of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonyl phenyl ether) phosphoric acid sodium hydroxide Neutralized product 1.0 part (c) BA 50.0 parts St 10.0 parts AMA 0.4 parts 1,3BD 0.14 parts tHH 0.2 parts Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% Neutralized product of a mixture of sodium hydroxide with 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid and 1.0 part (d) MMA 57.0 parts M A 3.0 parts nOM 0.3 parts tBH 0.06 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 combined product (MMA / MA = 98/2, reduced viscosity 0.06 L / g) was mixed at a ratio shown in Table 1 using a Henschel mixer. Next, using a 40 mmφ screw type twin screw 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., pelletized, and formed into a pellet made of the composition 1 for a film. I got

The pellet was dried at 80 ° C. for 24 hours,
Using a 40 mmφ non-vent screw extruder (L / D = 26) equipped with a 00 mm T die, a 200 μm thick film at a cylinder temperature of 200 to 240 ° C., a T die temperature of 250 ° C., and a cooling roll temperature of 70 ° C. Was formed.

The obtained acrylic resin film was subjected to gravure printing, heated at 140 ° C. for 1 minute, and then vacuum-molded with a mold having a vacuuming function. Then, with the formed film placed in a mold, an ABS resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Diapet ABS Bulk Sum T)
M20) was injection molded on the printing surface side to obtain an acrylic laminated molded product.

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 and thermal deformation temperature of the obtained films, and Table 2 shows the physical properties of the films and the evaluation results of the surface hardness, plasticizer whitening resistance, moldability and the like of the molded products.

<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 An acrylic resin film and an acrylic laminate were prepared in the same manner as in Example 1 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 6 The thermoplastic polymer (I) was treated with M
Example 1 Except for changing to the MA / MA copolymer (MMA / MA = 90/10, reduced viscosity 0.06 L / g)
In the same manner as in Example 1, a film composition 5 was prepared, and an acrylic resin film and an acrylic laminated molded product were produced and evaluated in the same manner as in Example 1 except that this composition was used.

Example 7 A rubber-containing polymer obtained by polymerization of the rubber-containing polymer (II) -a of Example 1 by changing the composition of (b) to the following (e) (II)-
Except that b was used, a film composition 6 was prepared in the same manner as in Example 1, except that this composition was used.
In the same manner as in Example 6, an acrylic resin film and an acrylic laminated molded product were manufactured and evaluated. (E) MMA 22.3 parts BA 16.0 parts St 1.7 parts AMA 0.15 parts 1,3BD 1.2 parts tBH 0.18 parts Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% and di (Polyoxyethylene nonyl phenyl ether) 1.0 part of a partially neutralized product of a mixture of 60% phosphoric acid and sodium hydroxide.

Example 8 In the polymerization of the rubber-containing polymer (II) -a of Example 1, the composition (b) was changed to the following (f) to obtain a rubber-containing polymer. (II)-
Except that c was used, a film composition 7 was prepared in the same manner as in Example 6, except that this composition was used.
An acrylic resin film and an acrylic laminated molded product were manufactured and evaluated in the same manner as in Example 6. (F) MMA 20.2 parts BA 18.0 parts St 1.8 parts AMA 0.15 parts 1,3BD 1.2 parts tBH 0.18 parts Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% and di (Polyoxyethylene nonyl phenyl ether) 1.0 part of a partially neutralized product of a mixture of 60% phosphoric acid and sodium hydroxide.

<Example 9> In the polymerization of the rubber-containing polymer (II) -a in Example 1, the composition of (b) was changed to the following (g) to obtain a rubber-containing polymer. (II)-
Except for using d, a film composition 8 was prepared in the same manner as in Example 6, except that this composition was used.
An acrylic resin film and an acrylic laminated molded product were manufactured and evaluated in the same manner as in Example 6. (G) MMA 18.6 parts BA 20.0 parts St 1.4 parts AMA 0.15 parts 1,3BD 1.2 parts tBH 0.18 parts Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% and di (Polyoxyethylene nonyl phenyl ether) 1.0 part of a partially neutralized product of a mixture of 60% phosphoric acid and sodium hydroxide.

<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.
However, in Comparative Example 1, a sample could not be obtained because the film-forming property of the film was poor. Regarding Comparative Example 2, an acrylic resin film was prepared in the same manner as in Example 1 except that the film composition 9 was prepared as described above, and this composition was used.
An acrylic laminated molded product was manufactured and evaluated.

Comparative Example 3 In the polymerization of the rubber-containing polymer (II) -a of Example 1, the composition of (b) was changed to the following (h) to obtain a rubber-containing polymer. (II)-
A film composition 10 was prepared in the same manner as in Example 1 except that e was used, and an acrylic resin film and an acrylic laminated molded product were produced in the same manner as in Example 1 except that this composition was used. And evaluated. (H) BA 32.0 parts St 8.0 parts AMA 0.4 parts 1.3BD 0.14 parts tBH 0.18 parts Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% and di (polyoxyethylene nonyl) Phenyl ether) Partial neutralized product of a mixture of 60% sodium hydroxide and phosphoric acid 1.0 part.

<Comparative Example 4> In the polymerization of the rubber-containing polymer (II) -a of Example 1, the rubber-containing polymer was obtained by changing the composition of (ii) to the following (ii). (II)-
Except that f was used, a film composition 11 was prepared in the same manner as in Example 1, and an acrylic resin film and an acrylic laminated molded product were produced in the same manner as in Example 1 except that this composition was used. And evaluated. (I) MMA 40.0 parts AMA 0.4 parts 1.3BD 0.14 parts tBH 0.18 parts Mono (polyoxyethylene nonyl phenyl ether) phosphoric acid 40% and di (polyoxyethylene nonyl phenyl ether) phosphoric acid 1.0 part of a partially neutralized mixture of 60% sodium hydroxide.

Comparative Example 5 In the polymerization of the rubber-containing polymer (II) -a of Example 1, the amount of the emulsifier of the raw material (B) was changed so that the final particle size of the latex was 0.12 μm. A rubber-containing polymer (II) -g was obtained. An attempt was made to form a film in the same manner as in Example 1 except that the rubber-containing polymer (II) -g having an average particle size of 0.12 μm was used. I couldn't.

[0082]

[Table 1]

[0083]

[Table 2]

<Evaluation> From the evaluation of Examples and Comparative Examples,
The following has been found. . All of the films of Examples 1 to 9 have good film-forming properties,
It has transparency, surface hardness, plasticizer whitening resistance, and vacuum moldability. . In particular, in the film of Example 8, disappearance of whitening generated immediately after molding in the corner whitening property evaluation during vacuum molding is earlier than that of the film of Example 6. . Particularly, since the film of Example 9 does not cause whitening after molding in the evaluation of the corner portion whitening property during vacuum molding, it can be applied to a deep drawn molded article requiring moldability, and has an industrial value. high. . Since the content of the elastic polymer (II) and the elastic polymer ((II-A) + (II-B)) is small in the film of Comparative Example 1, the film-forming properties of the film are poor. . Although the film of Comparative Example 2 has good vacuum moldability and film formability, it has a large content of the elastic polymer (II) and the elastic polymer ((II-A) + (II-B)). Since the whitening resistance of the plasticizer is poor and there is a limitation in the application in which it is used, its industrial utility value is low. . Although the film of Comparative Example 3 has good vacuum moldability and film formability, the glass transition temperature of the innermost layer polymer (II-A) is low, so the plasticizer whitening resistance is poor and used. The industrial use value is low because the use is restricted. . Although the film of Comparative Example 4 has excellent plasticizer whitening resistance, the innermost layer polymer (II-A) has a high glass transition temperature, and thus is inferior in corner whitening and followability during vacuum forming. Such a film having poor secondary processability has a narrow range of processing conditions when used as a film for injection molding, and is limited in the shape of an acrylic laminated molded product, and thus has low industrial utility value. . In the film of Comparative Example 5, the particle size of the rubber-containing polymer (II) was small, so that the film-forming property of the film was poor.

[0085]

As described above, according to the present invention,
It is possible to obtain an acrylic resin film as a substitute for coating and an acrylic laminated molded product, which have both plasticizer whitening resistance and moldability.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA33 AA77 AA80 AA83 AF25 AF45 BC01 BC02 4F100 AK25A AK25J AK45 AK74 AL01A AL05A AL09A AT00C BA03 BA07 BA10A BA10C DE01A EC04 EH17 EH36 GB33 HB31B013J05J05B05J05B05J05B05 BG063 BN122 FD05 GL00 GN00 GR00

Claims (7)

[Claims] 1. A thermoplastic polymer (I) 7 shown below
5 to 94.5 parts by mass and 5.5 to 5 parts of the rubber-containing polymer (II)
An elastic polymer ((II-A) + (II-A) comprising the innermost polymer (II-A) and the rubber polymer (II-B) in the rubber-containing polymer (II). B)) amount of 5
18 parts by mass [total of component (I) and component (II) 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) The innermost layer polymer having a glass transition temperature of 0 ° C or higher and lower than 25 ° C obtained by polymerizing a monomer containing an alkyl methacrylate and an alkyl acrylate as the innermost layer (II- A) wherein the intermediate layer has a glass transition temperature of 0 obtained by polymerizing a monomer containing an alkyl acrylate.
The outermost layer is composed of a rubber polymer (II-B) having a temperature lower than 0 ° C., and the outermost layer is composed of an outermost layer polymer (II-C) obtained by polymerizing a monomer containing an alkyl methacrylate. A rubber-containing polymer having an average particle size of 0.2 to 0.4 μm. 2. A thermoplastic polymer (I) 6 shown below:
5 to 94.4 parts by mass, rubber-containing polymer (II) 5.5 to 25
Parts by mass and 0.1 to 10 parts by mass of the thermoplastic polymer (III), from the innermost layer polymer (II-A) and the rubber polymer (II-B) in the rubber-containing polymer (II). 5 to 18 parts by mass of the elastic polymer ((II-A) + (II-B)) [total of the components (I), (II) and (III) is 1
00 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) The innermost layer polymer having a glass transition temperature of 0 ° C or higher and lower than 25 ° C obtained by polymerizing a monomer containing an alkyl methacrylate and an alkyl acrylate as the innermost layer (II- A) wherein the intermediate layer has a glass transition temperature of 0 obtained by polymerizing a monomer containing an alkyl acrylate.
The outermost layer is composed of a rubber polymer (II-B) having a temperature lower than 0 ° C., and the outermost layer is composed of an outermost layer polymer (II-C) obtained by polymerizing a monomer containing an alkyl methacrylate. A rubber-containing polymer having an average particle size of 0.2 to 0.4 μm. 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 according to claim 1, which has a pencil hardness (measured based on JIS K5400) of H or more. 4. The acrylic resin film according to claim 1, which has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. 5. The acrylic resin film according to claim 1, wherein a picture is printed on one side. 6. An acrylic laminated molded product obtained by laminating the acrylic resin film according to claim 1 on a substrate. 7. The acrylic resin film according to claim 1, which is obtained by subjecting the acrylic resin film according to claim 1 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.