JP3479645B2 - Acrylic resin film for paint replacement and acrylic laminated molded product using this - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an acrylic laminated molded article obtained by laminating a specific acrylic resin film for coating substitution,
Also, the present invention relates to an acrylic resin film as a paint substitute used for manufacturing such a molded article.

[0002]

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

As a method other than the above, there is an in-mold molding method as a method of imparting a design property to a molded product at low cost. This method is to insert a sheet or film of printed polyester resin, polycarbonate resin, acrylic resin, etc. into a three-dimensional shape by vacuum molding or the like in advance, or insert it into an injection molding die without molding. The resin as the base material is injection molded. In the in-mold molding, a resin sheet or film may be integrated with a base resin, or only printing may be transferred. Acrylic resin films suitable for in-mold molding are disclosed in JP-A-8-323934 and JP-A-11-147237. Such an acrylic resin film not only imparts a decorative property to a molded product, but is also used as an alternative material for clear coating.

Further, JP-A-2000-167869, JP-A-2000-178365, and JP-A-20-2000.
No. 00-178399 discloses an acrylic resin film that 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, a member formed by an in-mold forming method and having an acrylic resin film layer on its surface has been used for automobile interiors.

For example, in JP-A-8-323934, by using a rubber-containing polymer having a specific particle size in a smaller amount than before, an acrylic resin film having excellent surface hardness, heat resistance and moldability can be obtained. Have 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 the member on which the film is laminated, there is a problem that whitening occurs due to aging.

Further, for example, JP-A-11-147237 proposes to use a rubber-containing polymer having a hard core structure having a glass transition temperature of about 105 ° C. With this method, an acrylic resin film having excellent surface hardness can be obtained, but there is a problem that the moldability is poor because the elastic modulus is higher than that of the soft core rubber. Specifically, because the film is hard, the trim end surface during film formation becomes unstable, the preheating time during vacuum forming becomes long and productivity deteriorates, whitening occurs at the corners, There is a problem that the followability of the film to the mold of some part is deteriorated and the film is cracked when taken out from the mold.

Further, JP-A 2000-167869, JP-A 2000-178365, and JP-A 20-2000.
All of the acrylic resin films described in JP-A-00-178399 have a glass transition temperature of 20 ° C. inside the rubber layer.
A rubber elastic body having the above polymer is used. However, substantially, like the rubber-containing polymer described in JP-A No. 11-147237, the glass transition temperature is about 10
Since it relates to a rubber elastic body having a hard core structure having a 5 ° C. innermost layer polymer, it has the same problem as the technique described in JP-A No. 11-147237.

An object of the present invention is to solve these problems of the prior art. Specifically, it is a substitute for coating which is compatible with plasticizer whitening resistance and moldability without impairing 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 As a result of intensive studies to solve the above problems, the present inventors have identified a rubber-containing polymer having a specific structure and a specific thermoplastic polymer as a specific polymer. It was found that the acrylic resin film contained in a ratio has a very excellent effect, and the present invention has been completed.

That is, the present invention comprises 75 to 94.5 parts by mass of the thermoplastic polymer (I) and 5.5 to 25 parts by mass of the rubber-containing polymer (II) shown below. An elastic polymer ((II-A) + (II) composed of the innermost layer polymer (II-A) and the rubber polymer (II-B) in (II).
The amount of (B)) is 5 to 18 parts by mass [total 100 parts by mass of the component (I) and the component (II)]. Thermoplastic polymer (I) methacrylic acid alkyl ester 50 to 100% by mass,
Acrylic acid alkyl ester 0 to 50% by mass and other vinyl monomers 0 to 49% by mass copolymerizable with these, reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 mL of chloroform, Measured at 25 ° C) is 0.1 L / g
The following are thermoplastic polymers. Rubber-containing polymer (II) The innermost layer having a glass transition temperature of 0 ° C or higher and lower than 25 ° C, obtained by polymerizing a monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester (II- A), wherein the intermediate layer has a glass transition temperature of 0 obtained by polymerizing a monomer containing an alkyl acrylate.
A three-layer structure consisting of a rubber polymer (II-B) having a temperature of less than 0 ° C. and an outermost layer comprising an outermost layer polymer (II-C) obtained by polymerizing a monomer containing an alkyl methacrylate. A rubber-containing polymer having an average particle diameter of 0.2 to 0.4 μm.

The present invention further relates to the above-mentioned thermoplastic polymer (I) 65 to 94.4 parts by mass, and the rubber-containing polymer (I
I) 5.5 to 25 parts by mass, and 0.1 to 10 parts by mass of the thermoplastic polymer (III) shown below, and the innermost layer polymer (II- in the rubber-containing polymer (II). A) and an elastic polymer ((II-A) + composed of a rubber polymer (II-B)
The amount of (II-B)) is 5 to 18 parts by mass [total 100 parts by mass of the component (I), the component (II) and the component (III)]. . Thermoplastic polymer (III) consisting of 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 which is dissolved in 0 mL and measured at 25 ° C.) exceeds 0.2 L / g.

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

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polymer (I) used in the present invention is a methacrylic acid alkyl ester 50-100.
Mass% and 0 to 50 mass% of acrylic acid alkyl ester
And 0 to 49% by mass of other vinyl monomer copolymerizable with them, and the reduced viscosity of the polymer (measured at 25 ° C. by dissolving 0.1 g of the polymer in 100 mL of chloroform) is 0.1 L. / G or less of the thermoplastic polymer.

The reduced viscosity of the thermoplastic polymer (I) is 0.1.
When the content is L / g or less, an appropriate elongation occurs when the film raw material resin is melted, and the film forming property becomes good. The lower limit value of the reduced viscosity is preferably 0.05 L / g or more. When it is 0.05 L / g or more, the problem of film breakage during film formation and printing due to the brittleness of the film is less likely to occur.

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

Examples of the alkyl acrylate used as necessary in 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 the other copolymerizable vinyl monomer which is optionally used in the thermoplastic polymer (I), various conventionally known monomers can be used. Other vinyl monomers are used within the range of 0 to 49% by mass.

The thermoplastic polymer (I) is formed by polymerizing these monomers. The polymerization method is not particularly limited and may be suspension polymerization, emulsion polymerization, bulk polymerization or the like. A chain transfer agent may be used to bring the reduced viscosity of the polymer within a predetermined range. As the chain transfer agent, various conventionally known ones can be used, but mercaptans are particularly preferable. The amount of chain transfer agent used must be appropriately determined depending on the type and composition of the monomer.

The rubber-containing polymer (II) used in the present invention is
A plasticizer is an important component for achieving both whitening resistance and moldability, and is preferably a graft copolymer having a three-layer structure containing an alkyl acrylate as a main component of rubber.

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

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

An elastic polymer ((II-A) + (II-) consisting of the innermost layer polymer (II-A) and the rubber polymer (II-B).
In obtaining B)), vinyl monomers other than the acrylic acid alkyl ester and the methacrylic acid alkyl ester can be copolymerized. As the vinyl monomer, styrene, acrylonitrile and the like are preferable.

In order to obtain the elastic polymer ((II-A) + (II-B)), a copolymerizable crosslinkable monomer is usually 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,
Examples thereof include diallyl maleate, trimethylolpropane triacrylate, and allyl cinnamate. These may be used alone or in combination of two or more.

The use of this copolymerizable crosslinkable monomer is preferable because it can reduce the whitening caused by the swelling of the rubber due to the plasticizer contained in the resin that comes into contact with the film.

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

The innermost layer polymer (II-A) is necessary for developing the plasticizer whitening resistance of the film. The glass transition temperature of this innermost layer polymer (II-A) is 0 ° C or higher and 25 ° C or higher.
Is less than. When the glass transition temperature is lower than 0 ° C, the plasticizer whitening resistance of the film is inferior, and when it exceeds 25 ° C, the formability of the film during vacuum forming is inferior, so that the industrial utility value is lowered in any case. From the viewpoint of the 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, the glass transition temperature of the innermost layer polymer (II-A) is preferably 24 ° C. or lower, more preferably 10 ° C. or lower from the viewpoint of moldability during vacuum forming. Considering 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 higher and lower than 25 ° C., and 15
More preferably, the temperature is not less than 0 ° C and not more than 24 ° C.

The outermost layer polymer (II-C) is obtained by graft-polymerizing a monomer containing an alkyl methacrylate as a main component in the presence of an elastic polymer ((II-A) + (II-B)). Can be formed. The amount of the methacrylic acid alkyl ester used is preferably 50% by mass or more in the monomer used for the outermost layer polymer (II-C). Examples of the methacrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid 2
-Ethylhexyl, cyclohexyl methacrylate, etc. may be mentioned.

In obtaining the outermost layer polymer (II-C), other vinyl monomers copolymerizable with the methacrylic acid alkyl ester can be used in combination. Other vinyl monomers include, but are not particularly limited to, alkyl acrylates such as methyl acrylate, butyl acrylate, 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 used in an amount of 10 parts with respect to 100 parts by mass of the elastic polymer ((II-A) + (II-B)).
To 400 parts by mass, more preferably 20 to 200 parts by mass. The lower limit of these ranges is significant in that aggregation of the elastic polymer is less likely to occur and transparency is improved. The outermost layer polymer (II-
The polymerization for obtaining C) can be carried out in at least one step.

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

The rubber-containing polymer (II) can be produced by conventionally known emulsion polymerization or the like. The polymerization temperature at that time is
Depending on the type and amount of the polymerization initiator used, 40 to
120 ° C, preferably 60 to 95 ° C.

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

As the emulsifier, anionic, cationic or nonionic surfactants can be used. Anionic surfactants are particularly preferable. Examples of anionic surfactants include potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate, sulfate ester salts such as sodium lauryl sulfate, and dioctyl sulfosuccinate. Examples thereof include sodium acid salts, sodium dodecylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate-based sulfonates, and polyoxyethylene alkylphenyl ether sodium phosphate-based phosphate ester salts.

For the polymer latex obtained by the emulsion polymerization method, various conventionally known coagulation methods such as acid coagulation method, salt coagulation method, freeze coagulation method and spray drying method can be used. 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, and as the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium chloride. Organic salts such as calcium acetate and magnesium acetate can be used. The rubber-containing polymer (II) can be obtained by further washing, dehydrating and drying the solidified polymer.

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 the polymer is dissolved in 100 mL of chloroform). , Measured at 25 ° C.) is more than 0.2 L / g.

In the present invention, the thermoplastic polymer (III)
The use of (1) improves the film-forming property of the film, and is useful particularly 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.
When the range is more than 2 L / g, a film having good thickness accuracy can be obtained. This reduced viscosity is usually 0.
More than 2 L / g and 2 L / g or less, preferably 1.2 L / g
g or less.

Other vinyl-based monomers copolymerizable with methyl methacrylate, which are optionally used in the thermoplastic polymer (III), include acrylic acid alkyl esters, methacrylic acid alkyl esters, and aromatic vinyl compounds. , Vinyl cyanide compounds and the like.

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

In the case where the thermoplastic polymer (III) is not used, the acrylic resin film of the present invention has a thermoplasticity of 100 parts by mass based on the total amount of the thermoplastic polymer (I) and the rubber-containing polymer (II). The main component is 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).

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

In the case where the thermoplastic polymer (III) is not used, the acrylic resin film of the present invention is thermoplastic based on a total of 100 parts by weight of the thermoplastic polymer (I) and the rubber-containing polymer (II). The main component is 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).

When the thermoplastic polymer (III) is used, the thermoplastic polymer (I) and the rubber-containing polymer (II) are used.
And, based on a total of 100 parts by mass of the thermoplastic polymer (III), 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 The main component is 0.1 to 10 parts by mass of the plastic polymer (III). In this case, the thermoplastic polymer (II
When the amount of I) used is 0.1 part by mass or more, the effect of improving the film-forming property is exhibited, while when it is 10 parts by mass or less, the viscosity of the resin composition is suppressed and the film-forming property of the film is improved. It is possible to prevent deterioration and deterioration of transparency.

The amount of the elastic polymer ((II-A) + (II-B)) in the rubber-containing polymer (II) is 100 parts by weight of the total of the components (I) and (II), or , Component (I), component (II) and component (III) based on 100 parts by mass in total, 5 to 18 parts by mass, preferably 8 to 12 parts by mass. By setting this amount to 5 parts by mass or more, the film is less likely to become brittle and the film forming property is improved. Further, when the amount is 18 parts by mass or less, the transparency of the film is improved and the surface hardness required for the paint substitute film is obtained.

The acrylic resin film of the present invention contains, if necessary, common compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers, colorants, and gloss. A quencher, an ultraviolet absorber, etc. may be included. Particularly, from the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. UV absorber has a molecular weight of 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, it is possible to prevent mold stains and the like due to volatilization of the ultraviolet absorber during vacuum forming or pressure forming in an injection molding die. The type of the ultraviolet absorber is not particularly limited, but a benzotriazole type having a molecular weight of 400 or more or a triazine type having a molecular weight of 400 or more can be particularly preferably used. The former commercially available product is Tinubin 234 under the trade name of Ciba Geigy, the Adeka Stab LA-31 under the trade name of Asahi Denka Co., Ltd., and the commercially available product of the latter is Tinuvin 1577 under the Ciba Geigy company.
Etc.

The heat distortion temperature (measured according to ASTM D648) of the acrylic resin film of the present invention is preferably 80 ° C. or higher. When the heat distortion 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 it is used for a vehicle, if the heat distortion temperature is 100 ° C. or higher, it can be used near the handle part, and if it is 110 ° C. or higher, it can be used near the meter panel part. Therefore, the industrial utility value is high.

The heat distortion temperature of the acrylic resin film of the present invention varies depending on the amount of the rubber-containing polymer (II) used, but is mainly determined by the heat distortion 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. Depending on various conditions, for example, when using methyl acrylate as a polymerization component, the methyl methacrylate content 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 higher. In order to set the heat distortion temperature to 100 ° C. or higher, the content of methyl methacrylate in the thermoplastic polymer (I) can be adjusted to 95% by mass or higher. In order to set the heat distortion 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 set to 80 ° C. or higher or 100 ° C. or higher, it is possible to copolymerize maleimides such as maleic anhydride and phenylmaleimide to reduce the methyl methacrylate content accordingly.

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 calender method. In terms of economy,
The T-die method is particularly preferable.

Further, as the acrylic resin film as a paint substitute, a film which is printed by an appropriate printing method is used, if necessary, in order to impart a design property to the molded product. In this case, it is preferable that the acrylic resin film is subjected to a printing treatment on one side and used as a film having a pattern or the like printed on one side. Further, it is preferable to arrange the printing surface on the surface laminated with the base resin at the time of molding from the viewpoint of protecting the printing surface and imparting a high-class feeling. Further, when it is used as a substitute for transparent coating by making the best use of the color tone of plastic or the like as a base material, it can be used as it is as it is. In particular, for the purpose of utilizing the color tone of the substrate, the acrylic resin film is superior to the vinyl chloride or polyester film in terms of transparency, a feeling of depth, a feeling of high quality and the like.

Further, the acrylic resin film of the present invention can be used after being matt or colored if necessary.

The thickness of the acrylic resin film is not particularly limited, but is preferably 300 μm or less, and 100 μm to
300 μm is more preferable. When the thickness is 100 μm or more, the appearance of the molded product has a sufficient sense of depth, and particularly when the molded product is molded into a complicated shape, a sufficient thickness can be obtained. In addition, the upper limit of these ranges is that rigidity is moderately suppressed to maintain good laminating property and secondary workability, that mass per unit area is suppressed to maintain economic efficiency, and film forming property is stable. It is significant in terms of manufacturing a film.

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

An acrylic resin film used as a paint substitute 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 melt adhesion or the like. Specifically, it is preferable that the acrylic resin film is obtained by subjecting an acrylic resin film to vacuum molding or pressure molding in an injection molding die, and then injection molding a resin as a base material.

The resin constituting the substrate 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 main components can be used. 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, and ABS is particularly preferable.
A resin, a polycarbonate resin, or a resin containing these as a main component is more preferable. However, even a resin such as a polyolefin resin which is not melt-fused can be used as a base material. In this case, the acrylic resin film and the resin base material may be adhered at the time of molding by using a layer for adhesion.

In order to obtain a two-dimensional acrylic laminated molded article, an acrylic resin film may be laminated by a conventionally known laminating method such as thermal lamination. It is also possible to bond the base material that is not heat-sealed with an adhesive.

In order to obtain a three-dimensionally shaped acrylic laminated molded article, the laminate molding may be carried out 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 heating the acrylic resin film, vacuum molding is performed in a mold having a vacuuming function. This method is excellent in workability and economical efficiency because the film molding and the injection molding can be performed in one step. The heating temperature is preferably equal to or higher than the 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, but usually 7
It is 0 ° C or higher. Further, 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, the film is formed into a film by vacuum forming.
When imparting a three-dimensional shape, it is important to whiten the mold corners and to follow the corners, and this is a processing method that maximizes the characteristics of the acrylic resin film for coating alternative of the present invention. That is, the acrylic resin film of the present invention is rich in elongation at high temperature, which is very advantageous in such a case. Further, according to the in-mold molding method, after the three-dimensional shape is imparted to the film by vacuum molding in this way, the acrylic resin film and the base resin are melt-integrated by injection molding to form an acrylic resin film layer on the surface layer. It is possible to obtain an acrylic laminated molded product having

The industrial use of the acrylic laminated molded article of the present invention is not particularly limited, but 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 components that have been previously painted, such as building materials,
It has a very high utility value in these applications.

[0061]

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

With respect to the thermoplastic polymers (I) and (III), the rubber-containing polymer (II), and the film, various physical properties were measured by the following test methods. 1) Dissolve 0.1 g of the reduced viscosity polymer of the thermoplastic polymer (I) or (III) in 100 mL of chloroform,
It was measured at 5 ° C. 2) Average particle size of rubber-containing polymer (II) The final particle size of the polymer latex of the rubber-containing polymer (II) obtained by emulsion polymerization was measured with a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd. It was used and measured by the dynamic light scattering method. 3) Glass transition temperature DSC of polymer (DSC200 manufactured by Seiko Instruments Inc.)
Was measured using the obtained powder of the rubber-containing polymer (II) to determine the glass transition temperatures of the innermost layer polymer (II-A) and the rubber polymer (II-B). . However, the glass transition temperatures of the polymers in the rubber-containing polymers (II) -b and (II) -c used in Comparative Examples are the same as those obtained by salting out the latex at the time when the polymerization is completed. Was used to make measurements. 4) Total light transmittance and haze value of the film were evaluated according to JIS K6714. 5) Surface gloss of the film The surface gloss at 60 ° was measured using a gloss meter (GM-26D type manufactured by Murakami Color Research Laboratory). 6) Pencil hardness of the molded product It was evaluated according to JIS K5400. 7) Film-forming property A film having a thickness of 100 μm was formed by the T-die method, and a film that could be formed for 5 hours or more without being cut is indicated by “○”, and the film can be cut several times in 5 hours. The generated one was marked with “Δ”, and the one where no sample was obtained due to the cutting of the film was marked with “x”. 8) Heat distortion temperature of the film composition Pellets of the film composition are subjected to ASTM by injection molding.
Molded into a sample for heat distortion temperature measurement based on D648, 80 ℃
After annealing for 24 hours at low load (0.45 MPa)
It was measured according to STM D648. 9) Plasticizer-resistant Whitening of soft vinyl chloride resin using DOP as a plasticizer in a 20 ° C atmosphere for one month and observing the degree of whitening. The case where slight whitening was observed was designated as “Δ”, and the case where whitening was observed was designated as “x”. 10) Formability / film whitening at corners Whiteness of corners when vacuum forming was evaluated, and “○” means no whitening, and “○” means whitening immediately after molding but disappears thereafter. "B" indicates that the whitening did not disappear, and "X" indicates the whitening remained.・ Corner film conformability The moldability of the corner part when performing in-mold molding was evaluated. If there is no particular problem, "○" is indicated, and there is a part of the corner part that is not in contact with the mold during vacuum forming. However, if the injection molding was successful, there was no problem, and if the corners were not in contact with the mold at the time of vacuum molding and the film was broken when injection molding was performed, the film was torn. .

Example 1 a) Production of rubber-containing polymer (II) -a In 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., (a) shown below was added, and 1/15 of a mixture of the following raw materials (b) (raw materials for the polymer (II-A)) while stirring. Charge 15
Held minutes. Then, the remaining raw material (b) was continuously added at an increase rate of 8% / hour of the monomer mixture with respect to water. Then, the mixture was maintained for 1 hour to obtain a latex of 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. in a nitrogen atmosphere while the following raw materials (c) (rubber polymer ( The raw material of II-B) was continuously added at an increase rate of 4% / hour of the monomer mixture with respect to water. After that, the rubber polymer (II-B) is kept for 2 hours to polymerize the rubber polymer (II-B) to give an elastic polymer ((II-A) +
A latex of (II-B)) was obtained.

To this latex was subsequently added 0.4 parts of sodium formaldehyde sulfoxylate to give 15
While maintaining the content for 20 minutes and stirring at 80 ° C. under a nitrogen atmosphere, the following raw material (d) (raw material for the outermost layer polymer (II-C)) is added at an increase rate of 10% / hour of the monomer mixture to water. Was continuously added. After that, the rubber-containing polymer (II) is retained by holding it for 1 hour to carry out the outermost layer polymer (II-C).
-A latex was obtained. The rubber-containing polymer (II) -a had an average particle diameter of 0.28 μm.

The rubber-containing polymer (II) -a latex was subjected to coagulation, aggregation and solidification reaction using calcium acetate, filtered, washed with water and dried to obtain the rubber-containing polymer (I).
I) -a was obtained. (B) Sodium formaldehyde sulfoxylate 0.6 parts Ferrous sulfate 0.0002 parts Disodium ethylenediaminetetraacetate 0.0003 parts (b) MMA 22.0 parts BA 15.0 parts St 3.0 parts AMA 0 0.4 parts 1,3BD 0.14 parts tBH 0.18 parts Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% and di (polyoxyethylene nonylphenyl ether) phosphoric acid 60% Sodium hydroxide part Neutralized product 1.0 parts (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% Partially neutralized product of a mixture of sodium hydroxide with 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid 1.0 part (d) MMA 57.0 parts MA 3.0 parts nO 0.3 parts tBH 0.06 parts.

B) Production of thermoplastic polymer (III) A reactor was charged with 200 parts of nitrogen-exchanged deionized water, 1 part of emulsifier potassium oleate and 0.3 part of potassium persulfate. Then MMA 40 parts, BA10
Part, nOM 0.005 part were charged, and under a nitrogen atmosphere at 65 ° C.
The mixture was stirred for 3 hours to complete the polymerization. Then, M
A monomer mixture consisting of 48 parts of MA and 2 parts of BA was added dropwise over 2 hours, and after the completion of the addition, the mixture was maintained for 2 hours to complete the polymerization and obtain a latex of the thermoplastic polymer (III). This latex was added to a 0.25% aqueous solution of sulfuric acid to acid-coagulate the polymer, which was then dehydrated, washed with water and dried 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 Rubber-containing polymer (II) -a and thermoplastic polymer (III) obtained as described above, and MMA / MA copolymerization as thermoplastic polymer (I) The combined product (MMA / MA = 98/2, reduced viscosity 0.06 L / g) was mixed using a Henschel mixer at a ratio shown in Table 1. Then, 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 pellets composed of the composition 1 for film. Got

The pellets were dried at 80 ° C. for one day and then dried.
A film having a thickness of 200 μm at a cylinder temperature of 200 ° C. to 240 ° C., a T die temperature of 250 ° C., a cooling roll temperature of 70 ° C., using a 40 mmφ non-vent screw extruder (L / D = 26) equipped with a 00 mm T die. Was formed into a film.

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

As for the film forming property, as described above, 100 μ
A film having a thickness of m was formed and judged. Table 1 shows film-forming properties and heat distortion temperature of the obtained film, and Table 2 shows evaluation results of physical properties of the film and surface hardness of molded products, plasticizer whitening resistance, moldability and the like.

<Examples 2, 3, 4> The blending amounts of the thermoplastic polymer (I), the rubber-containing polymer (II) -a and the thermoplastic polymer (III) were changed as shown in Table 1. Film compositions 2, 3 and 4 were prepared in the same manner as in Example 1 except for using these, and an acrylic resin film and an acrylic laminate molded article were produced 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 base material to be injection-molded was changed to polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd., trade name Iupilon S100). Molded articles were manufactured and evaluated.

Example 6 The thermoplastic polymer (I) was mixed with M
Example 1 except that the MA / MA copolymer (MMA / MA = 90/10, reduced viscosity 0.06 L / g) was used.
A film composition 5 was prepared in the same manner as above, and an acrylic resin film and an acrylic laminate molded article 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 polymerizing the rubber-containing polymer (II) -a of Example 1 by changing the composition of (B) to (E) shown below. (II)-
A film composition 6 was prepared in the same manner as in Example 1 except that b was used, and except that this composition was used,
An acrylic resin film and an acrylic laminated molded product were produced and evaluated in the same manner as in Example 6. (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 nonylphenyl ether) 1.0 part of a partially neutralized product of a mixture of sodium hydroxide with 60% phosphoric acid.

Example 8 A rubber-containing polymer obtained by polymerizing the rubber-containing polymer (II) -a of Example 1 by changing the composition of (B) to (F) shown below. (II)-
A film composition 7 was prepared in the same manner as in Example 6 except that c was used, and except that this composition was used,
An acrylic resin film and an acrylic laminated molded product were produced 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 nonylphenyl ether) 1.0 part of a partially neutralized product of a mixture of sodium hydroxide with 60% phosphoric acid.

Example 9 A rubber-containing polymer obtained by polymerizing the rubber-containing polymer (II) -a of Example 1 by changing the composition of (B) to (G) shown below. (II)-
A film composition 8 was prepared in the same manner as in Example 6 except that d was used, and except that this composition was used,
An acrylic resin film and an acrylic laminated molded product were produced 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 diester. (Polyoxyethylene nonylphenyl ether) 1.0 part of a partially neutralized product of a mixture of sodium hydroxide with 60% phosphoric acid.

<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.
A film was formed in the same manner as in Example 1, but in Comparative Example 1, the film forming property of the film was poor and a sample could not be obtained. For 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 and the composition was used as described above.
An acrylic laminated molded article was manufactured and evaluated.

Comparative Example 3 A rubber-containing polymer obtained by polymerizing the rubber-containing polymer (II) -a of Example 1 by changing the composition of (B) to (H) shown below. (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 article 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) 1.0 part of a partially neutralized mixture of sodium hydroxide with 60% phosphoric acid.

Comparative Example 4 A rubber-containing polymer obtained by polymerizing the rubber-containing polymer (II) -a of Example 1 by changing the composition of (b) to (i) shown below. (II)-
A film composition 11 was prepared in the same manner as in Example 1 except that f was used, and an acrylic resin film and an acrylic laminated molded article 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 nonylphenyl ether) phosphoric acid 40% and di (polyoxyethylene nonylphenyl ether) phosphoric acid 1.0 part of partially neutralized product of a mixture of 60% sodium hydroxide.

Comparative Example 5 In the polymerization of the rubber-containing polymer (II) -a of Example 1, the amount of emulsifier of the raw material (B) was changed so that the final particle size of the latex would be 0.12 μm. A rubber-containing polymer (II) -g was obtained. A film was formed in the same manner as in Example 1 except that this rubber-containing polymer (II) -g having an average particle diameter of 0.12 μm was used, but the film-forming property of the film was poor, and a sample was obtained. I couldn't do it.

[0082]

[Table 1]

[0083]

[Table 2]

<Evaluation> From the evaluation of Examples and Comparative Examples,
The following was found. ． The films of Examples 1 to 9 all have good film-forming properties,
It has transparency, surface hardness, plasticizer whitening resistance and vacuum formability. ． In particular, in the film of Example 8, the whitening generated immediately after molding disappeared earlier in the corner whitening evaluation during vacuum forming than the film of Example 6. ． Further, in particular, the film of Example 9 does not cause whitening after forming in the evaluation of whitening at the corner portion during vacuum forming, so that it can be applied to a deep-drawing-shaped formed product that requires formability and has industrial utility value. high. ． The film of Comparative Example 1 has a low content of the elastic polymer (II) and the elastic polymer ((II-A) + (II-B)), so that the film forming property of the film is poor. ． The film of Comparative Example 2 has good vacuum formability and film-forming property, but since the content of the elastic polymer (II) and the elastic polymer ((II-A) + (II-B)) is high, Poor whitening resistance of plasticizers, resulting in limited applications and low industrial utility value. ． The film of Comparative Example 3 has good vacuum formability and film-forming property, but since the glass transition temperature of the innermost layer polymer (II-A) is low, it has poor plasticizer whitening resistance and is used. Its industrial utility value is low because its use is limited. ． Although the film of Comparative Example 4 is excellent in plasticizer whitening resistance, it is inferior in corner part whitening property and followability during vacuum forming because the glass transition temperature of the innermost layer polymer (II-A) is high. As described above, a film having poor secondary processability has a narrow range of processing conditions when used as a film for injection molding, and the shape of an acrylic laminated molded product is limited, so that the film has low industrial utility value. ． In the film of Comparative Example 5, the rubber-containing polymer (II) has a small particle size, and therefore the film-forming property of the film is poor.

[0085]

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

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Claims (7)

(57) [Claims] 1. A thermoplastic polymer (I) 7 shown below.
5-94.5 parts by mass and rubber-containing polymer (II) 5.5-
An elastic polymer ((II-A) + (II-) containing 25 parts by mass of the innermost polymer (II-A) and the rubber polymer (II-B) in the rubber-containing polymer (II). The amount of B)) is 5 to
18 parts by mass [total of component (I) and component (II) 100
Parts by weight]. An acrylic resin film as a paint substitute. Thermoplastic polymer (I) methacrylic acid alkyl ester 50 to 100% by mass,
Acrylic acid alkyl ester 0 to 50% by mass and other vinyl monomers 0 to 49% by mass copolymerizable with these, reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 mL of chloroform, Measured at 25 ° C) is 0.1 L / g
The following are thermoplastic polymers. Rubber-containing polymer (II) The innermost layer having a glass transition temperature of 0 ° C or higher and lower than 25 ° C, obtained by polymerizing a monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester (II- A), wherein the intermediate layer has a glass transition temperature of 0 obtained by polymerizing a monomer containing an alkyl acrylate.
A three-layer structure consisting of a rubber polymer (II-B) having a temperature of less than 0 ° C. and an outermost layer comprising an outermost layer polymer (II-C) obtained by polymerizing a monomer containing an alkyl methacrylate. A rubber-containing polymer having an average particle diameter 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
From 0.1 to 10 parts by mass of the thermoplastic polymer (III) and the innermost layer polymer (II-A) and the rubber polymer (II-B) in the rubber-containing polymer (II). The amount of the elastic polymer ((II-A) + (II-B)) is 5 to 18 parts by mass [total of component (I), component (II) and component (III) 1
00 parts by weight]. An acrylic resin film as a paint substitute. Thermoplastic polymer (I) methacrylic acid alkyl ester 50 to 100% by mass,
Acrylic acid alkyl ester 0 to 50% by mass and other vinyl monomers 0 to 49% by mass copolymerizable with these, reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 mL of chloroform, Measured at 25 ° C) is 0.1 L / g
The following are thermoplastic polymers. Rubber-containing polymer (II) The innermost layer having a glass transition temperature of 0 ° C or higher and lower than 25 ° C, obtained by polymerizing a monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester (II- A), wherein the intermediate layer has a glass transition temperature of 0 obtained by polymerizing a monomer containing an alkyl acrylate.
A three-layer structure consisting of a rubber polymer (II-B) having a temperature of less than 0 ° C. and an outermost layer comprising an outermost layer polymer (II-C) obtained by polymerizing a monomer containing an alkyl methacrylate. A rubber-containing polymer having an average particle diameter of 0.2 to 0.4 μm. Thermoplastic polymer (III) consisting of 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 which is dissolved in 0 mL and measured at 25 ° C.) exceeds 0.2 L / g. 3. The acrylic resin film according to claim 1, which has a pencil hardness (measured according to JIS K5400) of H or more. 4. The acrylic resin film according to claim 1, which has a heat distortion temperature (measurement based on ASTM D648) of 80 ° C. or higher. 5. The acrylic resin film according to claim 1, wherein a pattern is printed on one side. 6. An acrylic laminated molded article, comprising the acrylic resin film according to claim 1 or 2 laminated on a substrate. 7. The acrylic resin film according to claim 1 or 2, which is obtained by subjecting the acrylic resin film to vacuum molding or pressure molding in an injection mold, and then injection molding a resin as a base material. Acrylic laminated products.