JP2022111655A - Resin composition, film and molding - Google Patents

Abstract

To provide a resin composition which can reduce a fish eye causing poor appearance of a film and is excellent in fine matting properties, transparency and chemical resistance, and to provide a film using the same, and a molding.SOLUTION: A resin composition contains a fluorine-based resin, a first polymer, a second polymer and a third polymer, wherein the first polymer is a polymer having a reactive group; the second polymer is a polymer that has 30 mass% or more of alkyl (meth)acrylate whose ester group has 1 or more and 3 or less carbon atoms as a constitutional unit and does not substantially have a reactive group; the third polymer is a polymer that has 30 mass% or more of alkyl (meth)acrylate whose ester group has 4 or more carbon atoms as a constitutional unit and does not substantially have a reactive group, and the second polymer and the third polymer have different compositions.SELECTED DRAWING: None

Description

The present invention relates to resin compositions, films and molded articles.

Fluorine-based films composed of fluorine-based resins represented by vinylidene fluoride-based resins have excellent weather resistance, chemical resistance, and stain resistance. It is widely used as a protective film laminated on the surface of various substrates such as Also, substrates whose surfaces are protected with fluorine-based films are used in many applications such as interior and exterior materials for buildings, furniture, and interior and exterior materials for automobiles.

In recent years, in particular, a high-grade appearance has been emphasized, and the use of products laminated with a fluorine-based matte film is increasing.

The matte film is mainly produced by (1) a method of applying fine unevenness to the film surface by means of a mat roll made of metal or rubber with a roughened surface, followed by thermoforming; (3) a method of coating a film with a matting agent; and (4) a fine organic or inorganic filler (matting agent) to form a film. It is known to add it to the resin for use.

In the above method (1), there is a problem that additives such as ultraviolet absorbers added to the fluororesin clog the mat roll. There is a problem that it is difficult to In the method (2), there is a problem that the treated film stretches or breaks during sandblasting. In method (3), since the matting agent is non-stick (non-adhesive) to the fluorine-based resin, it is difficult to coat the surface of the fluorine-based resin with the matting agent.

As a case of using an inorganic matting agent in the method (4), Patent Document 1 proposes a matte fluorine film in which inorganic fine particles are dispersed in a vinylidene fluoride resin.

As a case where an organic matting agent is used in the method (4), Patent Document 2 proposes a surface protective film for interior and exterior building materials containing a crosslinked acrylic resin having a specific particle size in a vinylidene fluoride resin. ing. Further, Patent Document 3 discloses a matte fluorine film in which a fluorine-based resin contains a non-crosslinked acrylic resin.

JP-A-2002-80674 Japanese Unexamined Patent Application Publication No. 2008-7709 WO2011/093300

The film obtained in Patent Document 1 has excellent chemical resistance and matting properties, but the presence of an inorganic matting agent during melt extrusion accelerates the decomposition of the resin, resulting in poor appearance such as foaming and coloring of the resulting film. problems may occur. Also, the film obtained in Patent Document 2 is excellent in weather resistance and matting properties, but it cannot be said that the chemical resistance is sufficient. The film obtained in Patent Document 3 is excellent in matting properties and chemical resistance, but has a problem of frequent occurrence of foreign matter defects called fish eyes. When fluorine-based films are used for applications such as interior and exterior materials for automobiles, in addition to chemical resistance and matte properties, higher quality is required, and in particular, there are many requests for reducing fisheyes. .

An object of the present invention is to provide a resin composition, a film using the same, and a molded product that can reduce fisheyes that cause poor appearance of the film and have fine matte properties, transparency, and excellent chemical resistance. to provide.

As a result of intensive studies by the present inventors, it was found that by adding two or more kinds of specific acrylic polymers to the resin composition, it is possible to reduce fisheyes, which cause poor film appearance, and to achieve fine-textured matting and transparency. The present inventors have found that a resin composition having excellent properties and chemical resistance, and a fluorine-based film, a fluorine-based laminated film, and a laminated molding using the same can be obtained.

That is, the present invention has the following features.
[1] A resin composition containing a fluororesin, a first polymer, a second polymer, and a third polymer, wherein the first polymer has a reactive group wherein the second polymer has 30% by mass or more of (meth)acrylic acid alkyl ester having 1 to 3 carbon atoms in the ester group as a structural unit, and is substantially reactive It is a polymer having no group, and the third polymer has 30% by mass or more of (meth)acrylic acid alkyl ester having 4 or more carbon atoms in the ester group as a structural unit, and substantially A resin composition which is a polymer having no reactive group, wherein the second polymer and the third polymer have different compositions.
[2] The resin composition according to [1], wherein the third polymer has a weight average molecular weight of 50,000 to 500,000.
[3] further comprises, as structural units, a methacrylic acid alkyl ester having an ester group having 1 to 3 carbon atoms and a (meth)acrylic acid alkyl ester having an ester group having a carbon number of 4 to 18, and substantially The resin composition according to [1] or [2], which contains a fourth polymer having no reactive group.
[4] The resin composition according to any one of [1] to [3], wherein the weight average molecular weight of the fourth polymer is 500,000 or more and 5,000,000 or less.
[5] The ratio of the fluororesin to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 40% by mass or more and 98% by mass. The resin composition according to [1] to [4] below.
[6] The ratio of the first polymer to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 1% by mass or more. The resin composition according to any one of [1] to [5], which is 20% by mass or less.
[7] The ratio of the second polymer to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 1% by mass or more. The resin composition according to any one of [1] to [6], which is 40% by mass or less.
[8] The ratio of the third polymer to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 0.1 mass % or more and 10% by mass or less, the resin composition according to any one of [1] to [7].
[9] The resin composition according to any one of [1] to [8], wherein the fluororesin is polyvinylidene fluoride.
[10] The resin composition according to any one of [1] to [9], wherein the first polymer is an acrylic polymer.
[11] selected from the group consisting of reactive groups, carboxy groups, hydroxy groups, acid anhydride groups, epoxy groups, isocyanate groups, amide groups, amino groups, cyano groups and imine groups possessed by the first polymer; The resin composition according to any one of [1] to [10], which is one or more.
[12] A film comprising the resin composition according to any one of [1] to [11].
[13] A molded article having the film according to [12].

INDUSTRIAL APPLICABILITY According to the present invention, a resin composition that can reduce fish eyes that cause poor appearance of the film and has fine matte properties, transparency, and excellent chemical resistance, a fluorine-based film using the same, a fluorine-based laminated film, and It becomes possible to provide a laminate molded body.

Embodiments of the present invention will be described in detail below, but the present invention is not limited to these descriptions, and other than the following examples may be appropriately modified within the scope of the present invention.
In this specification, (meth)acryl means acrylic or methacrylic, and (meth)acrylic acid ester means acrylic acid ester or methacrylic acid ester. In this specification, the term "~" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.

The resin composition according to this embodiment includes at least a fluororesin, a first polymer, a second polymer, and a third polymer. The first polymer is a polymer having a reactive group, and the second polymer contains 30% by mass or more of a methacrylic acid alkyl ester having an ester group having 1 or more and 3 or less carbon atoms as a structural unit. and is a polymer that does not substantially have a reactive group, and the third polymer contains 30% by mass or more of a (meth)acrylic acid alkyl ester having an ester group having 4 or more carbon atoms as a structural unit. and substantially no reactive groups, and the second polymer and the third polymer are polymers having different compositions.

[Fluorine resin]
The fluorine-based resin is not particularly limited, and examples thereof include ethylene-tetrafluoroethylene-based copolymers, polychlorotrifluoroethylene, polytetrafluoroethylene, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, Examples include tetrafluoroethylene-perfluoro(propyl vinyl ether) copolymers and vinylidene fluoride polymers. These may be used individually by 1 type, and may use 2 or more types together. Among them, the vinylidene fluoride polymer is preferable from the viewpoint of the light transmittance of the film to be obtained, the ability to develop a fine matte texture, and the compatibility between the fluororesin and the first polymer.

The vinylidene fluoride-based polymer may be a resin containing vinylidene fluoride units, and examples thereof include homopolymers consisting only of vinylidene fluoride units and copolymers containing vinylidene fluoride units. The content of vinylidene fluoride units relative to the total number of repeating units of the vinylidene fluoride polymer is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, in order to improve chemical resistance. Preferably, 90 mol % or more is more preferred, and 100 mol %, ie polyvinylidene fluoride, is most preferred.

Other vinyl monomers copolymerizable with vinylidene fluoride include, for example, fluorinated vinyl monomers such as vinyl fluoride, ethylene tetrafluoride, ethylene trifluorochloride, and propylene hexafluoride; styrene; , ethylene, butadiene, propylene, and (meth)acrylic acid esters.

In addition, the fluorine-type resin can also use a commercial item. Examples of commercially available products include KFT#850 (trade name) manufactured by Kureha Corporation; Kynar720 and Kynar710 (trade names) manufactured by Arkema Corporation.

The vinylidene fluoride copolymer may be used alone or in combination of two or more.

The mass average molecular weight (Mw) of the fluororesin is not particularly limited, but is preferably 20,000 or more, more preferably 50,000 or more, from the viewpoint of chemical resistance. From the viewpoint of film formability, the mass average molecular weight (Mw) of the fluororesin (A) is preferably 1,000,000 or less, more preferably 7,000,000,000 or less. In addition, in this invention, the mass average molecular weight (Mw) of a compound shows the value obtained by measuring on the following conditions by a gel permeation chromatography (GPC).

<GPC measurement conditions>
Equipment used: HLC-8320GPC system manufactured by Tosoh Corporation Column (guard): TGKgel SuperGuardH-H (manufactured by Tosoh Corporation, trade name)
Column (main): 2 TGKgel SuperHZM-H (manufactured by Tosoh Corporation, trade name) Eluent: DMF containing 0.01 mmol/L LiCl
Column temperature: 40°C
Detector: Differential refractive index (RI)

The fluorine-based resin is not particularly limited, but the MFR measured under the conditions of a temperature of 230° C. and a load of 49 N is preferably 5 g/10 min or more, more preferably 6 g/10 min or more, and further preferably 7 g/10 min or more. On the other hand, it is preferably 40 g/10 min or less, more preferably 35 g/10 min or less, even more preferably 30 g/10 min or less. If the MFR of the fluororesin (A) is 5 g/10 min or more, the moldability is excellent, and if it is 40 g/10 min or less, the process stability is excellent.

The melting point of the fluorine-based resin is not particularly limited, but is preferably 100° C. or higher, more preferably 120° C. or higher, from the viewpoint of heat resistance, and is preferably 190° C. or lower, and 180° C. or lower from the viewpoint of transparency. is more preferred.

The refractive index of the fluorine-based resin is not particularly limited, but is preferably 1.30 or more, more preferably 1.40 or more, and preferably 1.60 or less, and 1.50 or less, in order to improve transparency. is more preferred. In order to improve transparency, the refractive index of the fluororesin (A) is preferably close to the refractive index of the acrylic resin (C) described later. Specifically, the difference is 0.25. It is preferably 0.15 or less, more preferably 0.15 or less.

[First polymer]
The first polymer is not particularly limited as long as it is a polymer having a reactive group. As described above, the first polymer having a reactive group can function as a delustering agent that suppresses the luster of the film or molded article obtained using the resin composition according to the present embodiment and improves the appearance.

The first polymer is not particularly limited, and examples thereof include polystyrene, polyvinyl chloride, AS resin, ABS resin, acrylic resin, polycarbonate, modified polyphenylene ether, etc., having a reactive group. These may be used individually by 1 type, and may use 2 or more types together.

The reactive group means a group that allows the first polymer to react with each other, and is not particularly limited, but is preferably a carboxy group, a hydroxyl group, an acid anhydride group, an epoxy group, an isocyanate group, an amide group, An amino group, cyano group, imine group, sulfonic acid group, aziridine group, amine group, urea group, phosphoric acid group, cyanate group, imidazole group or oxazoline group.

In addition, the reactive group which the 1st polymer has should just have in the monomer part which comprises this polymer. That is, in order to produce the first polymer having the desired reactive group, it can be obtained by polymerizing the monomer having the desired reactive group. That is, it can be obtained by polymerizing a monomer having a reactive group. The first polymer having a reactive group is a homopolymer of a monomer having a reactive group, a copolymer of two or more kinds having a reactive group, a monomer having a reactive group and a reactive group. may be a copolymer with a monomer having no

Among these, the first polymer is preferably a copolymer of a monomer having a reactive group and a monomer having no reactive functional group.

Among the above, the first polymer is preferably a (meth)acrylic polymer having a reactive group from the viewpoint of compatibility with the fluororesin.

A (meth)acrylic polymer is a polymer mainly composed of (meth)acrylic monomer units. The (meth)acrylic monomer unit preferably contains 50% by mass or more of a (meth)acrylic acid alkyl ester unit. Above all, from the viewpoint of compatibility between the fluororesin and the first polymer, the total content of (meth)acrylic acid alkyl ester units with respect to the total amount of the first polymer is more preferably 70% by mass or more.

When the first polymer is a (meth)acrylic polymer, the (meth)acrylic polymer may be a homopolymer of a (meth)acrylic acid alkyl ester, or a plurality of (meth)acrylic It may be a copolymer of an acid alkyl ester, or a copolymer of a (meth)acrylic acid ester and another monomer. Other monomers include, but are not limited to, (meth)acrylic acid, styrene, and the like.

Examples of (meth)acrylic monomers having a reactive group include (meth)acrylic acid hydroxyalkyl ester, acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, maleic acid, fumaric acid, crotonic acid, (Meth)acrylamide, diethylacrylamide, aminoethyl (meth)acrylate, glycidylalkyl (meth)acrylate, (meth)acryloyl isocyanate, cyanoethyl acrylate and the like. Among these, the first polymer is preferably a polymer containing a hydroxyl group as a reactive group from the viewpoint of improving the matte appearance of the resulting film or molded article. ) It is preferably a polymer having a hydroxyalkyl acrylate as a monomer unit.

Examples of (meth)acrylic acid hydroxyalkyl esters include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. is mentioned. These may be used individually by 1 type, and may use 2 or more types together. Among these, the (meth)acrylic acid hydroxyalkyl ester is preferably a (meth)acrylic acid hydroxyalkyl ester having an ester group having 1 or more carbon atoms, while an ester group having 8 or less carbon atoms ( It is preferably a hydroxyalkyl meth)acrylate, more preferably a hydroxyalkyl (meth)acrylate having an ester group having 6 or less carbon atoms, and a (meth)acrylic acid having an ester group having 4 or less carbon atoms. Acid hydroxyalkyl esters are more preferred, and 2-hydroxyethyl methacrylate is particularly preferred from the viewpoint of the most excellent matting property.

The monomer having no reactive functional group is not particularly limited, but includes (meth)acrylic acid alkyl ester having no reactive group.

The methacrylic acid alkyl ester having no reactive group is not particularly limited, and examples of the methacrylic acid alkyl ester having no reactive group include methyl methacrylate, ethyl methacrylate, n-methacrylate Examples include propyl, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate and t-butyl methacrylate. These may be used individually by 1 type, and may use 2 or more types together. Among them, methacrylic acid alkyl esters in which the ester group has 1 or more carbon atoms are preferred, while methacrylic acid alkyl esters in which the ester group has 13 or less carbon atoms are preferred, and the ester group has 9 carbon atoms. The following methacrylic acid alkyl esters are more preferable, and methacrylic acid alkyl esters in which the ester group has 6 or less carbon atoms are more preferable. Among them, methyl methacrylate is particularly preferable from the viewpoint of weather resistance.

Examples of alkyl acrylates having no reactive group include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, and acrylic acid. t-butyl and 2-ethylhexyl acrylate. These may be used individually by 1 type, and may use 2 or more types together. Among them, alkyl acrylates in which the ester group has 1 or more carbon atoms are preferred, while alkyl acrylates in which the ester group has 12 or less carbon atoms are preferred, and the ester group has 8 carbon atoms. The following alkyl acrylates are more preferred, and alkyl acrylates in which the ester group has 6 or less carbon atoms are even more preferred.

Among these, the first polymer is preferably a copolymer of a (meth)acrylic acid alkyl ester having a reactive group and a (meth)acrylic acid alkyl ester having no reactive group. Preferably, it is a copolymer of a reactive group, a (meth)acrylic acid alkyl ester, a methacrylic acid alkyl ester having no reactive group, and an acrylic acid alkyl ester having no reactive group. . The preferred form of each monomer is as described above.

When the first polymer is a (meth)acrylic polymer, the ratio of the (meth)acrylic acid alkyl ester having a reactive group to 100% by mass of the total monomer components constituting the polymer is It is preferably 5% by mass or more, more preferably 20% by mass or more, from the viewpoint that the matte property of the film obtained is good, and on the other hand, the dispersibility of the first polymer in the resin composition is good. is preferably 80% by mass or less, more preferably 50% by mass or less, from the viewpoint that the

The ratio of the methacrylic acid alkyl ester to 100% by mass of the total monomer components constituting the first polymer is preferably 20% by mass or more, more preferably 30% by mass or more, from the viewpoint of good weather resistance. , preferably 99% by mass or less, more preferably 90% by mass or less, in terms of matte expression.

The ratio of the alkyl acrylate to 100% by mass of the total monomer components constituting the first polymer is 0.5% by mass because the dispersibility of the first polymer in the resin composition is improved. 5% by mass or more is preferable, and 40% by mass or less is preferable, and 25% by mass or less is more preferable in terms of weather resistance and heat resistance.

As described above, the monomer unit having no reactive group includes (meth)acrylic acid alkyl ester having no reactive group. It may have a vinyl monomer unit having no functional group. Specifically, other vinyl monomers having no reactive group include aromatic vinyl compounds such as styrene, chlorostyrene, methylstyrene, and other substituted styrenes. These may be used individually by 1 type, and may use 2 or more types together. Although the content of other vinyl monomers having no reactive groups relative to 100% by mass of the total structural units constituting the first polymer is not particularly limited, the obtained film or molded article From the viewpoint of water whitening resistance, it is preferably 0% by mass or more, and preferably 50% by mass or less.

The glass transition temperature (Tg) of the first polymer is not particularly limited. 120° C. or less is preferable, and 110° C. or less is more preferable. On the other hand, the glass transition temperature (Tg) is preferably 50° C. or higher, particularly preferably 60° C. or higher, from the viewpoint of good water whitening resistance. The Tg of the first polymer is determined by FOX using the Tg value of the homopolymer of each monomer component (described in Polymer Handbook [Polymer Handbook, J. Brandrup, Interscience, 1989]). Calculated from the formula

The hydroxyl value of the first polymer is not particularly limited, but is preferably 50 mgKOH/g or more, more preferably 60 mgKOH/g or more, and is preferably 230 mgKOH/g or less, more preferably 200 mgKOH/g or less. If the hydroxyl value is 50 mgKOH/g or more, the first polymer becomes incompatible with the resin mixture of the fluororesin and the second polymer, and the obtained film or molded article has better matte. sexuality emerges. Moreover, if the hydroxyl value of the first polymer is 230 mgKOH/g or less, whitening of the film or molded article obtained when exposed to hot water is suppressed, which is preferable. The hydroxyl value is obtained by acetylating the hydroxyl groups in 1 g of the solid content of the vinyl polymer solution with acetic anhydride, and titrating the number of milligrams of potassium hydroxide required to neutralize the acetic acid produced by the acetylation. measured and calculated.

The intrinsic viscosity of the first polymer is not particularly limited. It is preferably 0.3 L/g or less, more preferably 0.15 L/g or less, in order to improve the appearance. In addition, the intrinsic viscosity of the first polymer is more preferably 0.05 L/g or more, more preferably 0.06 L/g or more, from the viewpoint of improving the matting properties of the resulting film or molded article. The intrinsic viscosity of the first polymer is a value measured at 25° C. using an AVL-2C automatic viscometer manufactured by Sun Electronics Industry using chloroform as a solvent.

Polymerization modifiers such as, for example, mercaptans can be used to adjust the intrinsic viscosity of the first polymer. Mercaptans include, for example, n-octylmercaptan, n-dodecylmercaptan, and t-dodecylmercaptan. The content of mercaptan is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the first polymer in terms of good dispersibility. In addition, it is preferably 1 part by mass or less from the viewpoint of improving the matting properties of the resulting film or molded article.

Mw/Mn, which is the ratio of the mass average molecular weight (Mw) to the number average molecular weight (Mn) of the first polymer, is preferably 2.3 or less, more preferably 2.2 or less. As this Mw/Mn is smaller, the molecular weight distribution of the first polymer becomes closer to monodisperse, so that the high molecular weight components are reduced and the occurrence of poor appearance due to foreign substances in the film is suppressed. In addition, Mw/Mn shows the value obtained by measuring on the following conditions by a gel permeation chromatography (GPC).

<GPC measurement conditions>
Equipment used: HLC-8320 GPC system manufactured by Tosoh Corporation Column: 2 TGKgel SuperHZM-H (manufactured by Tosoh Corporation, trade name) Eluent: Tetrahydrofuran Column temperature: 40°C
Detector: Differential refractive index (RI)

The Mw of the first polymer is preferably 30,000 or more, more preferably 50,000 or more, while it is preferably 250,000 or less, and more preferably 200,000 or less. If the Mw of the first polymer is 30,000 or more, the dispersibility in the resin composition will be better, while if it is 250,000 or less, it will be easy to develop a fine-textured matte appearance.

As a method for producing the first polymer, as described above, the polymer can be obtained by selecting monomers to be used so as to obtain a desired composition and polymerizing them. The polymerization method is not particularly limited, and includes suspension polymerization and emulsion polymerization. Examples of initiators used for suspension polymerization include known organic peroxides and azo compounds. Suspension stabilizers include known organic colloidal polymeric substances, inorganic colloidal polymeric substances, inorganic fine particles, and combinations thereof with surfactants. The inorganic suspension stabilizer is preferably one that can be removed by post-polymerization treatment such as washing, and examples thereof include tribasic calcium phosphate.

Suspension polymerization is usually carried out using an aqueous suspension of monomers and the like together with a polymerization initiator in the presence of a suspension stabilizer. Further, a polymer soluble in the monomer can be dissolved in the monomer and polymerized in the suspension polymerization, if necessary. After the suspension polymerization, it is preferable to remove cullet, which is a chloroform-insoluble component generated during the polymerization and causes poor appearance, from the beads obtained by the suspension polymerization by sieving. The sieve used for sieving is preferably 150 mesh or less, more preferably 50 mesh or less, in order to secure a sufficient yield. In order to sufficiently remove cullet, 50 mesh or more is preferable, and 150 mesh or more is more preferable. Cullet refers to lumps produced by a polymer adhering to a portion such as the inner wall surface of a polymerized layer that comes into contact with the latex during polymerization.

It is preferable that the first polymer does not contain cullet of 300 μm or more in order to reduce foreign matter in the resulting film or molded article and improve the appearance of the film or molded article. It is more preferable not to include cullet of 100 µm or more.

When an inorganic suspension stabilizer is used, the resulting first polymer beads are washed with water in order to suppress the occurrence of fisheyes in the resulting film and to suppress print defects. , it is preferable to reduce the content of inorganic substances in the first polymer. Examples of the water washing method include a dispersion washing method in which a washing liquid such as nitric acid is added to the thermoplastic resin beads for dispersion, followed by solid-liquid separation; washing method. The washing temperature is preferably 10 to 90° C. from the viewpoint of washing efficiency.

In post-treatments such as sieving and water washing after completion of polymerization as described above, in order to efficiently remove cullet by sieving without reducing the product yield, and to efficiently remove inorganic substances by washing. Therefore, the average particle size of the first polymer is preferably 300 μm or less, more preferably 150 μm or less. Moreover, the average particle size is preferably 10 μm or more, more preferably 20 μm or more, from the viewpoint of polymer handling properties. The average particle size of the first polymer can be measured using a laser diffraction/scattering particle size distribution analyzer LA-910 manufactured by HORIBA.

[Second polymer]
The second polymer has, as a structural unit, an ester group having 1 to 3 carbon atoms and 30% by mass or more of a (meth)acrylic acid alkyl ester unit having no reactive group, and substantially It is a polymer without reactive groups. In the present invention, substantially no reactive group means that the total proportion of the monomer having a reactive group in 100% by mass of the monomer component constituting the polymer is 1.0% by mass. shall mean that: The dispersibility of the first polymer in the film or molded article obtained by containing the second polymer in the resin composition is improved, foreign substances in the film or molded article are reduced, The effect of improving the appearance of the film can be expected.

Methacrylic acid alkyl esters having an ester group having 1 to 3 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate and i-propyl methacrylate. These may be used individually by 1 type, and may use 2 or more types together. Among them, methyl methacrylate is preferable from the viewpoint of weather resistance.

Examples of alkyl acrylates having 1 to 3 carbon atoms in the ester group include methyl acrylate, ethyl acrylate, n-propyl acrylate and i-propyl acrylate. These may be used individually by 1 type, and may use 2 or more types together.

Among the above, the second polymer is preferably a copolymer having a methacrylic acid alkyl ester and an acrylic acid alkyl ester as monomer units. In this case, the ratio of the methacrylic acid alkyl ester having 1 to 3 carbon atoms in the ester group to 100% by mass of the monomer component constituting the second polymer is preferably 50% by mass or more from the viewpoint of weather resistance. 85% by mass or more is more preferable, and 92% by mass or more is even more preferable.

From the standpoint of heat resistance, the proportion of the alkyl acrylate having 1 to 3 carbon atoms in the ester group in 100% by weight of the monomer component is preferably 0% by weight or more, more preferably 0.1% by weight or more. In terms of weather resistance, the ratio is preferably 50% by mass or less, more preferably 15% by mass or less, and even more preferably 8% by mass or less.

Also, the second polymer may have other vinyl monomers as monomer units. Specifically, other copolymerizable vinyl monomers include aromatic vinyl compounds such as styrene, chlorostyrene, methylstyrene and other substituted styrenes, and lower alkoxy acrylates. These may be used individually by 1 type, and may use 2 or more types together. The ratio of these vinyl monomers to 100% by mass of the total monomer units constituting the second polymer is preferably 0% by mass or more from the viewpoint of water whitening resistance of the film. % or less is preferable.

From the viewpoint of heat resistance, the glass transition temperature (Tg) of the second polymer is preferably 80°C or higher, more preferably 85°C or higher. From the viewpoint of moldability of the obtained film or molded article, the temperature is preferably 120° C. or lower, more preferably 110° C. or lower.

Polymerization methods for the second polymer include, for example, a suspension polymerization method, an emulsion polymerization method, and a bulk polymerization method.

The mass-average molecular weight (Mw) of the second polymer is preferably 10,000 or more, more preferably 30,000 or more, from the viewpoint of mechanical properties, while it is preferably 250,000 or less, and 200,000 or less from the viewpoint of formability of a film or molded article. is more preferred.

A commercial product can also be used as the second polymer. Commercially available products thereof include, for example, ACRYPET VH, ACRYPET MD and ACRYPET MF manufactured by Mitsubishi Chemical Corporation.

[Third polymer]
The third polymer is a polymer having 30% by mass or more of a (meth)acrylic acid alkyl ester having an ester group having 4 or more carbon atoms as a structural unit and having substantially no reactive group. , is a polymer having a different composition than the second polymer. By including the third polymer in the resin composition, the film-forming stability during molding can be improved, and fisheyes in the resulting film or molded article can be reduced. Although the mechanism by which the above effect can be expected by including the third polymer in the resin composition is not clear, the following reasons are conceivable.

The resin composition according to the present embodiment contains a fluororesin and a first polymer for the purpose of improving chemical resistance and matting function. However, as described above, since the first polymer has a reactive group, the first polymer reacts excessively with each other due to shear heat generation during melt extrusion when producing a film or the like, and the particle size When an abnormal polymer with a large .mu.m is formed, the dispersibility in the fluorine-based resin is lowered, and thermal deterioration of the resin is caused due to retention. As a result, the film formability of the film or the molded article is deteriorated, and further, fish-eye-like spots or foreign substances are formed in the obtained film or molded article. However, in the present embodiment, as described above, since the third polymer having a (meth)acrylic acid alkyl ester with a specific number of carbon atoms is contained as a monomer unit, the fluorine-based resin composition Lubricity can be improved, and as a result, shear heat generation during melt extrusion is reduced and excessive reaction of the first polymer is suppressed, thereby dispersing the first polymer in the fluororesin. Therefore, it is thought that it is possible to improve the stability of the film-forming property and to obtain a film or a molded article with few fish eyes.

Examples of alkyl acrylates having 4 or more carbon atoms in the ester group include n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and acrylic acid. phenyl, cyclohexyl acrylate and the like. Among these, alkyl acrylates in which the ester group has 18 or less carbon atoms are preferable, and alkyl acrylates in which the ester group has 8 or less carbon atoms are particularly preferable. In addition, these acrylic acid alkyl esters may be used individually by 1 type, and may use 2 or more types together.

Examples of methacrylic acid alkyl esters having an ester group having 4 or more carbon atoms include n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, and methacrylic acid. phenyl, cyclohexyl methacrylate, and the like. Among these, methacrylic acid alkyl esters in which the ester group has 18 or less carbon atoms are preferable, and methacrylic acid alkyl esters in which the ester group has 8 or less carbon atoms are particularly preferable. In addition, these methacrylic acid alkyl esters may be used individually by 1 type, and may use 2 or more types together.

Moreover, the third polymer may have other monomer units as the monomer units. Such other monomers include methacrylic acid alkyl esters having 1 to 3 carbon atoms.

Methacrylic acid alkyl esters having an ester group having 1 to 3 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate and i-propyl methacrylate. These may be used individually by 1 type, and may use 2 or more types together. Among them, methyl methacrylate is preferable from the viewpoint of weather resistance.

Among the above, the third polymer is n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate and i-butyl methacrylate, It is preferably a polymer having, as monomer units, at least one monomer selected from t-butyl methacrylate and 2-ethylhexyl methacrylate and methyl methacrylate. A polymer containing n-butyl acrylate, n-butyl methacrylate, and methyl methacrylate as monomer units is particularly preferred.

The total ratio of (meth)acrylic acid alkyl esters having 4 or more carbon atoms in the ester group with respect to 100% by mass of all monomer units constituting the third polymer is not particularly limited, but as described above, It is 30% by mass or more, preferably 40% by mass or more, preferably 70% by mass or less, and more preferably 60% by mass or less. If the ratio is 30% by mass or more, the resin composition can provide more lubricity, so shear heat generation during kneading in an extruder is suppressed, and the occurrence of fish eyes due to thermal deterioration of the resin is further reduced. be able to. Moreover, if this ratio is 70% by mass or less, the compatibility with the fluororesin is excellent, and the occurrence of fish eyes due to poor dispersion can be further reduced.

When the third polymer is composed of both an alkyl acrylate having 4 or more carbon atoms and an alkyl methacrylate having 4 or more carbon atoms as monomer units, is not particularly limited, but is preferably 20% by mass or more, particularly preferably 30% by mass or more, and preferably 80% by mass or less, and 70% by mass. % or less is particularly preferred.

The ratio of the methacrylic acid alkyl ester having 1 to 3 carbon atoms in the ester group with respect to 100% by mass of the total monomer units constituting the third polymer is not particularly limited, but in order to improve the weather resistance, , preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less for improving heat resistance.

The third polymer may contain other vinyl monomers. Specific examples include aromatic vinyl compounds such as styrene, chlorostyrene, methylstyrene and other substituted styrenes, and lower alkoxy acrylates. These may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of transparency of the film, the content of these other copolymerizable vinyl monomers should be 0% by mass or more with respect to 100% by mass of the total monomer units constituting the third polymer. is preferable, and on the other hand, it is preferably 20% by mass or less.

The mass average molecular weight (Mw) of the third polymer is not particularly limited, but is preferably 50,000 or more, more preferably 80,000 or more, and even more preferably 120,000 or more. Moreover, the mass average molecular weight (Mw) of the third polymer is preferably 5,000,000 or less, more preferably 4,000,000 or less, and even more preferably 3,500,000 or less. If the mass average molecular weight (Mw) is 50,000 or more, it is possible to impart greater lubricity to the resin composition, thereby suppressing shear heat generation during kneading in an extruder and preventing the occurrence of fish eyes due to thermal deterioration of the resin. In addition, blooming on the surface of the molded product and plate-out to the mold during molding are less likely to occur. On the other hand, if the mass average molecular weight (Mw) is 5,000,000 or less, the compatibility with the fluororesin is excellent, and the occurrence of fish eyes due to poor dispersion can be further reduced. In addition, the melt viscosity can be kept lower, and thermal deterioration of the resin due to retention in the molding machine can be suppressed. When the molded article to be obtained is a film, problems such as an increase in defects called fisheyes caused by heat deterioration over time are less likely to occur, and melt extrusion such as film molding is performed over a relatively long period of time. becomes possible.

A commercial item can also be used for the third polymer. Commercially available products include, for example, Metabrene L (trade name) manufactured by Mitsubishi Chemical Corporation.

The 5% weight loss temperature of the third polymer is not particularly limited, but is preferably 250° C. or higher, more preferably 260° C. or higher, and particularly preferably 270° C. or higher, in order to improve thermal stability.

The resin composition may contain two or more third polymers.

The resin composition may contain other components in addition to the fluororesin, the first polymer, the second polymer, and the third polymer. For example, the resin composition may contain a fourth polymer.
[Fourth polymer]
By including the fourth polymer (D) in the resin composition, film-forming stability can be improved and generation of die build-up can be suppressed when the resin composition is molded.

The fourth polymer contains, as structural units, a methacrylic acid alkyl ester having an ester group having 1 to 3 carbon atoms and a (meth)acrylic acid alkyl ester having an ester group having 4 or more carbon atoms, and substantially reacts It is a polymer with no functional groups.

Methacrylic acid alkyl esters having an ester group having 1 to 3 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate and i-propyl methacrylate. These may be used individually by 1 type, and may use 2 or more types together. Among them, methyl methacrylate is preferable from the viewpoint of weather resistance.

Examples of alkyl acrylates having 4 or more carbon atoms in the ester group include n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and acrylic acid. phenyl, cyclohexyl acrylate and the like. These may be used individually by 1 type, and may use 2 or more types together.

Examples of methacrylic acid alkyl esters having an ester group having 4 or more carbon atoms include n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, and methacrylic acid. phenyl, cyclohexyl methacrylate, and the like. These may be used individually by 1 type, and may use 2 or more types together.

The (meth)acrylic acid alkyl ester having an ester group having 4 or more carbon atoms is not particularly limited, but preferably has an ester group having 18 or less carbon atoms.

The ratio of methacrylic acid alkyl ester having 1 to 3 carbon atoms in the ester group in 100% by mass of the monomer component constituting the fourth polymer is preferably 70% by mass or more in terms of weather resistance, and 75% by mass. % or more is more preferable. In terms of heat resistance, the ratio is preferably 90% by mass or less, more preferably 80% by mass or less.

The ratio of (meth)acrylic acid alkyl ester having 4 or more carbon atoms in the ester group in 100% by mass of the monomer component constituting the fourth polymer is preferably 10% by mass or more from the viewpoint of heat resistance, 20% by mass or more is more preferable. Moreover, the ratio is preferably 30% by mass or less, more preferably 25% by mass or less, from the viewpoint of weather resistance.

Also, the fourth polymer may contain other copolymerizable vinyl monomers. Specific examples include aromatic vinyl compounds such as styrene, chlorostyrene, methylstyrene and other substituted styrenes, and lower alkoxy acrylates. These may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of water whitening resistance of the film, the content of these other copolymerizable vinyl monomers is 0 to 50% by mass with respect to 100% by mass of the monomer units constituting the fourth polymer. Preferably.

The mass average molecular weight (Mw) of the fourth polymer is not particularly limited, but is preferably 500,000 or more, more preferably 1,000,000 or more, while preferably 5,000,000 or less, more preferably 4,000,000 or less, and further preferably 3,500,000 or less. . When Mw is 500,000 or more, the resin composition has a large swell ratio, suppresses the occurrence of die buildup during film formation, and improves the appearance. Further, when the Mw is 5,000,000 or less, the obtained film has good transparency.

A commercial item can also be used for the fourth polymer. Examples of commercially available products include Metabrene P (trade name) manufactured by Mitsubishi Chemical Corporation; Kaneace PA (trade name) manufactured by Kaneka Corporation; and Acryloid (trade name) manufactured by Rohm and Haas.

In the resin composition, the content of the fluorine-based resin with respect to the total 100% by mass of the fluorine-based resin, the first polymer, and the second polymer is preferably 40% by mass or more, and is preferably 47% by mass or more. More preferably, 54% by mass or more is even more preferable. Also, the content is preferably 98% by mass or less, more preferably 97% by mass or less, and even more preferably 96% by mass or less. If the content of the fluororesin is 40% by mass or more, a film with more excellent chemical resistance can be obtained. If the content of the fluororesin is 98% by mass or less, yellowing of the film due to thermal deterioration of the resin can be further reduced.

In the resin composition, the content of the first polymer with respect to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 1.0. % by mass or more is preferable, 1.5% by mass or more is more preferable, and 2.0% by mass or more is even more preferable. Also, the content is preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less. When the content of the first polymer is 1.0% by mass or more, the obtained film can have a good matte appearance. When the content of the first polymer is 20% by mass or less, the fluidity and thermal stability during molding do not become too low, and thermal deterioration of the resin can be further suppressed.

In the resin composition, the content of the second polymer with respect to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 1.0. % by mass or more is preferable, 1.5% by mass or more is more preferable, and 2.0% by mass or more is even more preferable. Moreover, it is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less. When the content of the second polymer is 1.0% by mass or more, the dispersibility of the first polymer in the resin composition is further improved, and the occurrence of fish eyes due to poor dispersion can be further reduced. Further, when the content of the second polymer is 20% by mass or less, the resulting film has better chemical resistance.

In the resin composition, the content of the third polymer with respect to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is not particularly limited. However, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. Moreover, the content is preferably 10% by mass or less, more preferably 5.0% by mass or less. When the amount of the third polymer added is 0.1% by mass or more, lubricity can be imparted to the resin composition, so shear heat generation during kneading in an extruder can be suppressed, and fish due to thermal deterioration of the resin can be prevented. This is preferable because the occurrence of eyes can be further reduced. If the content of the third polymer is 10% by mass or less, the melt viscosity can be kept lower, and thermal deterioration of the resin due to retention in the molding machine can be further suppressed, which is preferable. When the molded article to be obtained is a film, problems such as an increase in defects called fisheyes caused by heat deterioration over time are less likely to occur, and melt extrusion such as film molding is performed over a relatively long period of time. It is possible.

In the resin composition, the content of the fourth polymer with respect to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is not particularly limited. is 0% by mass or more, preferably 1.0% by mass or more, and more preferably 2.0% by mass or more. Moreover, the content is preferably 20% by mass or less, more preferably 10% by mass or less. When the content of the fourth polymer is 1.0% by mass or more, it is preferable because the occurrence of die build-up in the film is suppressed and the appearance design of the film is improved. In addition, if the content of the fourth polymer is 20% by mass or less, it is preferable because fluctuations in the thickness of the film and poor appearance due to melt fracture do not occur.

Various additives can be blended into the resin composition of the present invention, if necessary. Examples of various additives include antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, spreading agents, antistatic agents, flame retardants, fillers, matting agents, processing aids, impact resistance aids, agents, antibacterial agents, antifungal agents, foaming agents, release agents, colorants, ultraviolet absorbers, thermoplastic polymers, and other additives.

Known ones can be used for these. Examples of antioxidants include phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants. Examples of heat stabilizers include hindered phenol-based heat stabilizers, sulfur-based heat stabilizers, and hydrazine-based heat stabilizers. Examples of plasticizers include phthalates, phosphates, fatty acid esters, aliphatic dibasic acid esters, oxybenzoic acid esters, epoxy compounds, and polyesters. Examples of lubricants include fatty acid esters, fatty acids, metallic soaps, fatty acid amides, higher alcohols, and paraffins. Examples of antistatic agents include cationic antistatic agents, anionic antistatic agents, nonionic antistatic agents, and amphoteric antistatic agents. Each of these additives may be used alone or in combination of two or more.

The resin composition can be produced by a known method such as a single-screw kneading method, a co-rotating twin-screw kneading method, or a counter-rotating twin-screw kneading method using an extruder, which is a general compounding process. Among them, a method with a large kneading effect such as a biaxial kneading method is preferable. Examples of the twin-screw extruder include the TEM series (trade name, manufactured by Toshiba Machine Co., Ltd.). In addition, as the screw configuration, the resin composition is kneaded such as a conveying section for conveying the resin composition, a kneading zone, and a screw segment whose melt feeding direction is opposite (screw segment whose spiral winding direction is opposite). A screw configuration having a kneading section for

Further, the extruder preferably has vents capable of degassing moisture in the raw material resin composition and volatile gas generated from the melted and kneaded material. Preferably, the vent is equipped with a pressure reducing pump such as a vacuum pump. This pump efficiently discharges generated moisture and volatile gas to the outside of the extruder. It is also possible to install a screen in front of the die portion of the extruder to remove foreign matter and the like mixed in during extrusion weight loss, thereby removing the foreign matter from the resin composition. Examples of the screen include wire mesh, filter packs using sintered metal nonwoven fabric, screen changers, leaf disc type and pleated type polymer filters, and the like.

Further, as a method for increasing the kneading effect, it is possible to raise the screw rotation speed as much as possible and reduce the supply amount of the resin composition. The resin composition melt-extruded in this way tends to generate shear heat, and the resin temperature at the head tends to rise. The melted material melted and kneaded in the extruder is extruded as a strand from a die having a nozzle with a diameter of about 3 to 5 mm installed in the head, cut by a cold cut method or a hot cut method, and pelletized. .

In addition, the number of times of kneading the resin composition is not limited, and kneading can be performed in one stage or in multiple stages by masterbatching.

The shape of the resin composition includes, for example, lumps, powders and pellets. Among these, pellets are preferred from the viewpoint of handleability of the resin composition.

In the present invention, the MFR (according to JIS K7210 A method) of the fluororesin, the first polymer and the second polymer for 4 minutes measured under the conditions of 200 ° C. and a load of 49 N are respectively MFR (A) , MFR(B) and MFR(C), it is preferable to satisfy the relationship "MFR(A)>MFR(B)≈MFR(C)". By satisfying this relationship, the dispersibility of the first polymer in the resin mixture of the fluororesin and the second polymer is improved during melt extrusion, and the matte stability of the film is improved. Note that MFR(B)≈MFR(C) means that the difference between MFR(B) and MFR(C) is within ±0.5 g/10 min. The MFR value is a value measured according to JIS K7210, and can be measured using a product name Melt Indexer manufactured by Techno Seven Co., Ltd., or the like.

[the film]
A film can be produced by molding the resin composition according to the present embodiment. That is, the film contains the resin composition according to the present embodiment, and the film has excellent matting properties and chemical resistance. In addition, since the production deviation of the matte appearance during film production is very small, the productivity in obtaining the film is good. Furthermore, since the occurrence of fisheyes during film production can be reduced, the obtained film is characterized by extremely few appearance defects.

In film performance evaluation, the 60-degree surface glossiness is used as an index indicating the luxury of the design. In general, a low 60 degree surface gloss is preferred. The 60-degree surface glossiness of the film is preferably 5% or more, more preferably 6% or more, and even more preferably 7% or more. The 60 degree surface glossiness is preferably 70% or less, more preferably 50% or less, and even more preferably 30% or less. If the 60-degree surface glossiness is 70% or less, the resulting film has matte properties, and is excellent in design properties such as a sense of luxury and depth, and decorative properties. Further, if the 60 degree surface glossiness is 5% or more, it is not necessary to add a large amount of delustering agent, and appearance defects such as fish eyes are reduced. The surface glossiness of the film is a value measured according to JIS Z8741.

The standard deviation of the 60-degree surface glossiness is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less, because production stability is improved and yield is improved.

The arithmetic mean roughness (Ra) of the film is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. Also, it is preferably 0.50 or less, more preferably 0.45 or less, and even more preferably 0.43 or less. If Ra is 0.05 or more, the feeling of glare is low, and the design and decoration properties, such as a feeling of luxury and depth, are excellent. When Ra is 0.50 or less, the matte texture is fine and the appearance design is excellent. The arithmetic mean roughness (Ra) is a value measured according to JIS B0601-2001.

The average length (Rsm) of the profile curve elements of the film is preferably 30 or more, more preferably 35 or more, and even more preferably 40 or more. Moreover, it is preferably 90 or less, more preferably 85 or less, and even more preferably 80 or less. If the Rsm is 30 or more, the feeling of glare is low, and the design and decoration properties such as a feeling of luxury and depth are excellent. If the Rsm is 90 or less, the matte texture is fine and the appearance design is excellent. The average length (Rsm) of profile elements is a value measured according to JIS B0601-2001.

As for the light transmittance of the film, the total light transmittance measured according to JIS K7361-1 is preferably 80% or more, more preferably 83% or more, and even more preferably 85% or more. If the total light transmittance is 80% or more, the decorative layer printed on the film is beautiful when viewed from the side on which the decorative layer is not printed.

The haze of the film is not particularly limited as long as the total light transmittance is 80% or more. From the viewpoint of beautiful appearance as a matte film, the haze is preferably 95% or less, more preferably 90% or less, and even more preferably 85% or less. The film haze is a value measured according to JIS K7136.

Regarding the number of fisheyes in the film, the number of fisheyes having a size of 0.05 mm ² or more in a film having a thickness of 40 μm is preferably 20/0.01 m ² or less, from the viewpoint of appearance design. /0.01 m ² or less.

The thickness of the film is preferably 1 μm or more, more preferably 5 μm or more, from the viewpoint of good film handling and laminating properties. In addition, from the viewpoint of good film-forming properties and processability, the thickness is preferably 500 μm or less, and more preferably 300 μm or less.

Examples of film production methods include melt extrusion methods such as a melt casting method, a T-die method, and an inflation method; and a calendering method. Among these, the T-die method is preferable in that it is economical. The film can be formed by a T-die method using an extruder or the like, and then wound around a tubular article such as a paper tube with a winder to form a roll-shaped article. In addition, uniaxial stretching (machine direction or transverse direction (direction perpendicular to the machine direction)), biaxial stretching (sequential biaxial stretching, simultaneous biaxial stretching), etc. by known stretching methods may be carried out as necessary during the film-forming process. A stretching step can be provided. In the case of melt extrusion, it is preferable to extrude while filtering the resin composition in a molten state through a screen mesh of 200 mesh or more in order to remove nuclei and foreign matter that cause poor appearance.

Moreover, a fine structure can also be formed on the film surface as needed. Methods for forming the fine structure include, for example, a thermal transfer method and an etching method. Among these, the thermal transfer method, in which a fine structure is formed on the surface of the film by heating a mold having a fine structure and then pressing the heated mold against the surface of the film, is advantageous in terms of productivity and economy. preferable. Examples of the thermal transfer method include the following methods (1) and (2).
(1) A method in which a mold having a fine structure is hot-pressed onto a film cut out from a roll-shaped article to thermally transfer the fine structure to a sheet.
(2) A continuous shaping method in which a film unwound from a roll-shaped article is sandwiched between a heated mold having a belt-like fine structure using nip rolls and pressurized to thermally transfer the fine structure to the surface of the film.

Examples of methods for manufacturing a mold having the fine structure include sandblasting, etching, and electrical discharge machining.

A film obtained from the resin composition according to the present embodiment can be combined with another film to form a laminated film. In particular, the film obtained from the resin composition according to this embodiment is preferably used as a laminated film with another acrylic resin layer. A specific form of such a laminated film will be described below. In the following, for convenience, the film obtained from the resin composition according to the present embodiment may be referred to as "film (X)", and the other acrylic resin layer may be referred to as "acrylic resin layer (Y)".

[Laminated film]
The laminated film is obtained by laminating the film (X) and the acrylic resin layer (Y). Such a laminated film is preferable because the moldability of the laminated film and the visibility of the decorative layer are improved. In addition to the acrylic layer, films made of other resins such as ionomer resins, polyolefin resins, silicone resins, epoxy resins, and polyurethane resins can also be used.

The layer thickness ratio of the film (X) and the acrylic resin layer (Y) (hereinafter referred to as "(X)/(Y)") affects the solvent resistance, cost, transparency and matte appearance of the laminated film. From this point of view, the value of (X)/(Y) is preferably 1/99 or more, more preferably 2/98 or more. In terms of surface hardness and printability, the value of (X)/(Y) is preferably 50/50 or less, more preferably 20/80 or less. The thickness of each film can be calculated by observing a sample obtained by cutting the laminated film in a thickness of 70 nm in the cross-sectional direction with a transmission electron microscope. Commercially available transmission electron microscopes include J100S (trade name) manufactured by JEOL Ltd., for example.

The 60-degree surface glossiness of the laminated film measured from the film (X) side is preferably 5% or more, more preferably 6% or more, and even more preferably 7% or more. The 60 degree surface glossiness is preferably 70% or less, more preferably 50% or less, and even more preferably 30% or less. If the 60-degree surface glossiness is 70% or less, the obtained film has good matte properties, and is excellent in design properties such as a sense of luxury and depth, and decorativeness. Further, if the 60 degree surface glossiness is 5% or more, it is not necessary to add a large amount of delustering agent, and appearance defects such as fish eyes are reduced.

The standard deviation of the 60-degree surface glossiness is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less, because production stability is improved and yield is improved.

The arithmetic mean roughness (Ra) of the laminated film measured from the film (X) side is preferably 0.05 or more, more preferably 0.10 or more, further preferably 0.15 or more, and 0.50 or less. is preferred, 0.45 or less is more preferred, and 0.43 or less is even more preferred. If Ra is 0.05 or more, the feeling of glare is low, and the design and decoration properties, such as a feeling of luxury and depth, are excellent. When Ra is 0.50 or less, the matte texture is fine and the appearance design is excellent. The arithmetic mean roughness (Ra) is a value measured according to JIS B0601-2001.

The average length (Rsm) of the contour element of the laminated film, measured from the film (X) side, is preferably 30 or more, more preferably 35 or more, and even more preferably 40 or more, while it is preferably 90 or less, and 85 or less. is more preferable, and 80 or less is even more preferable. If the Rsm is 30 or more, the feeling of glare is low, and the design and decoration properties such as a feeling of luxury and depth are excellent. If the Rsm is 90 or less, the matte texture is fine and the appearance design is excellent. The average length (Rsm) of profile elements is a value measured according to JIS B0601-2001.

As for the light transmittance of the laminated film, the total light transmittance measured according to JIS K7361-1 is preferably 80% or more, more preferably 83% or more, and even more preferably 85% or more. If the total light transmittance is 80% or more, the decorative layer printed on the film is beautiful when viewed from the side on which the decorative layer is not printed.

The haze of the laminated film is not particularly limited as long as the total light transmittance is 80% or more. % or less is more preferable

Regarding the surface hardness of the laminated film, it is preferable that the pencil hardness (JIS K5400) is higher than B when measured from the film (X) side. Furthermore, HB or more is more preferable, and F or more is most preferable. When a laminated film having a pencil hardness higher than B is used, it is less likely to be scratched during the process of insert molding or in-mold molding, which will be described later, and has good scratch resistance. When used for vehicle applications, the laminated film preferably has a pencil hardness of HB or higher. When the laminated film has a pencil hardness of HB or higher, the resulting laminate can be suitably used for various vehicle components such as door waist garnishes, front control panels, power window switch panels, and airbag covers. Furthermore, when the pencil hardness is higher than F, the scratch is hardly conspicuous even if it is scratched with a cloth having a rough surface such as gauze, so that the industrial utility value increases. The surface hardness of the laminated film can be adjusted by selecting the thickness ratio of the film (X) and the acrylic resin layer (Y) or the acrylic resin composition constituting the acrylic resin layer (Y), as described above. can be done.

From the viewpoint of appearance design, the number of fisheyes of the laminated film is 0.01 mm ² or more in a film with a thickness of 75 μm (film thickness ratio (X) / (Y) = 9/91). is preferably 100/0.5 m ² or less, more preferably 75/0.5 m ² or less, and even more preferably 50/0.5 m ² or less. The number of fisheyes of the laminated film can be measured by, for example, an off-line fisheye counter. Commercially available off-line fisheye counters include LSC-4500 (trade name) manufactured by MEC Co., Ltd.

The thickness of the laminated film is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 40 μm or more, from the viewpoint of good film handling and laminating properties. In addition, from the viewpoint of good film-forming property and processability, the thickness is preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 200 μm or less.

[Acrylic resin layer (Y)]
The acrylic resin layer (Y) is a layer made of the acrylic resin composition (y). As the acrylic resin composition (y), an acrylic resin composition containing a rubber-containing polymer is preferred.

The rubber-containing polymer includes, for example, a rubber-containing multistage polymer containing at least a known alkyl acrylate and/or alkyl methacrylate and a graft crossing agent as constituent components of the polymer.
Specific examples of the rubber-containing multistage polymer include at least an alkyl acrylate having an ester group having 1 to 8 carbon atoms and/or an alkyl methacrylate having an ester group having 1 to 4 carbon atoms, and a graft crossing agent. The elastic polymer (S) as a constituent component of the polymer and the hard polymer (H) at least as a constituent component of the methacrylic acid alkyl ester having 1 to 4 carbon atoms in the ester group are polymerized in this order. formed ones.

As the elastic polymer (S), for example, an alkyl acrylate having an ester group having 1 to 8 carbon atoms and/or an alkyl methacrylate having an ester group having 1 to 4 carbon atoms (S1) (hereinafter referred to as “component ( S1)”), another monomer (S2) used as necessary (hereinafter referred to as “component (S2)”), and a polyfunctional monomer (S3) used as necessary (hereinafter (referred to as "component (S3)") and a graft crossing agent (S4) (hereinafter referred to as "component (S4)") as constituent components, and is the first step in polymerizing a rubber-containing multistage polymer. It is polymerized to

Of the component (S1), the alkyl acrylate having an ester group with 1 to 8 carbon atoms may be linear or branched. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate. These may be used individually by 1 type, and may use 2 or more types together. Among these, those having a low Tg are preferred, and butyl acrylate is more preferred.

Of the component (S1), the methacrylic acid alkyl ester having an ester group having 1 to 4 carbon atoms may be linear or branched. Specific examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. These may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of flexibility, transparency and workability, it is preferable to use 60 to 100% by mass of component (S1) with respect to 100% by mass of components (S1) to (S4) in total.

Examples of the component (S2) include acrylic acid alkyl esters having an ester group having 9 or more carbon atoms, acrylic acid esters having an alkoxy group having 4 or less carbon atoms, acrylic acid alkyl ester monomers such as cyanoethyl acrylate; acrylamide; , (meth)acrylic acid, styrene, alkyl-substituted styrene, and (meth)acrylonitrile.

From the viewpoint of flexibility, it is preferable to use 0 to 40 mass % of component (S2) with respect to 100 mass % in total of components (S1) to (S4).

Examples of component (S3) include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate; divinylbenzene; , and trivinylbenzene.

From the viewpoint of flexibility, it is preferable to use 0 to 10% by mass of the component (S3) with respect to the total of 100% by mass of the components (S1) to (S4).

Component (S4) includes, for example, allyl, methallyl or crotyl esters of copolymerizable α,β-unsaturated carboxylic acids or dicarboxylic acids; triallyl cyanurate and triallyl isocyanurate. Among these, allyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid are preferred, and allyl methacrylate is more preferred.
Component (S4) is chemically bonded mainly by the conjugated unsaturated bond of its ester reacting much faster than the allyl group, methallyl group or crotyl group.

Component (S4) is preferably used in an amount of 0.1 to 5% by mass, more preferably 0.5 to 2% by mass, based on the total 100% by mass of components (S1) to (S4), from the viewpoint of flexibility. . The lower limits of these ranges are significant in terms of the effective amount of graft binding. Further, the upper limit value is significant in that the amount of reaction with the polymer to be polymerized next is appropriately suppressed, and the decrease in elasticity of the rubber elastic body is prevented.

The content of the elastic polymer (S) in the rubber-containing multistage polymer is preferably 5 to 70% by mass, more preferably 5 to 50% by mass, from the viewpoints of flexibility, transparency and workability.

The elastic polymer (S) may be polymerized in two or more stages. When polymerization is performed in two or more stages, the ratio of the monomer components constituting each stage may be changed.

The hard polymer (H) is a component involved in the moldability and mechanical properties of the rubber-containing multistage polymer, and is a methacrylic acid alkyl ester (H1) having 1 to 4 carbon atoms in the ester group (hereinafter referred to as "component (H1 )”) and another monomer (H2) used as necessary (hereinafter referred to as “component (H2)”) as constituent components, and polymerizes a rubber-containing multistage polymer. It is polymerized at the end of the process. Preferred specific examples of component (H1) and component (H2) are the same as those listed for components (S1) and (S2) of elastic polymer (S), respectively.

From the viewpoint of transparency, it is preferable to use 51 to 100% by mass of the component (H1) with respect to the total of 100% by mass of the components (H1) and (H2).

From the viewpoint of mechanical properties, the Tg of the hard polymer (H) alone is preferably 60°C or higher, more preferably 70°C or higher, and even more preferably 80°C or higher. From the viewpoint of film formability, Tg is preferably 150° C. or lower, more preferably 130° C. or lower.

The content of the hard polymer (H) in the rubber-containing multistage polymer is preferably 30 to 95% by mass, more preferably 40 to 70% by mass, from the viewpoints of flexibility, transparency and workability.

The rubber-containing multistage polymer has an elastic polymer (S) and a hard polymer (H) as basic structures. After polymerizing the elastic polymer (S), one or more layers of the intermediate polymer (M) may be polymerized before polymerizing the hard polymer (H). The intermediate polymer (M) has a composition intermediate between the composition of the elastic polymer (S) and the composition of the hard polymer (H). By providing the intermediate polymer (M), the transparency of the resulting film can be improved.

The content of the intermediate polymer (M) in the rubber-containing multistage polymer is preferably 0 to 35% by mass, more preferably 0 to 25%, based on the total 100% by mass of the elastic polymer (S) and the hard polymer (H). % by mass is more preferred.

The average particle size of the rubber-containing polymer is preferably 0.03 μm or more, more preferably 0.07 μm or more, from the viewpoint of the mechanical properties and transparency of the laminated film containing the acrylic resin layer (Y) containing the rubber-containing polymer as a main component. , and more preferably 0.09 μm or more. From the viewpoint of film transparency, the thickness is preferably 0.3 μm or less, more preferably 0.15 μm or less, and even more preferably 0.13 μm or less.

The mass average molecular weight (Mw) of the acetone-soluble portion of the rubber-containing polymer is preferably 20,000 or more, more preferably 30,000 or more. Moreover, 80,000 or less are preferable and 70,000 or less are more preferable. If Mw is 20,000 or more, the mechanical strength of the laminated film obtained is improved, and cracks during molding can be suppressed. In addition, the resulting laminated film exhibits stress whitening resistance. If the Mw is 80,000 or less, the resulting laminated film has high flexibility and excellent workability. After bonding the laminated film to a base material such as a steel plate, whitening does not occur at the bent portion during bending, and the appearance of various members obtained is improved.

The gel content of the rubber-containing polymer is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more. Moreover, it is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. If the gel content of the rubber-containing polymer is 40% by mass or more, the mechanical strength of the obtained molded article can be further increased, and handling becomes easier. In addition, if the gel content is 99% by mass or less, the fluidity and thermal stability during molding can be further increased, the melt viscosity can be kept lower, the retention in the molding machine can be reduced, and the heat of the resin can be reduced. It is preferable because deterioration can be suppressed. When the molded article to be obtained is a film, it is possible to perform melt extrusion such as film molding over a long period of time without causing problems such as an increase in fisheyes caused by heat deterioration over time.

Here, the gel content of the rubber-containing polymer can be calculated by the following formula.
G=(m/M)×100
In the formula, G (%) represents the gel content of the rubber-containing polymer, M represents the mass of a predetermined amount of rubber-containing polymer (also referred to as the pre-extraction mass), and m represents the predetermined amount of rubber-containing weight. The mass of the combined acetone-insoluble matter (also referred to as the post-extraction mass) is shown.
More specifically, m is dissolved in acetone at a concentration of 1 g/100 mL of the rubber-containing polymer, refluxed at 65° C. for 4 hours, centrifuged, and the residual solid was refluxed, centrifuged, and decanted again, It is obtained by drying the obtained solid at 50° C. for 24 hours.

The acrylic resin composition (y) may contain a thermoplastic resin. The thermoplastic resin is not particularly limited as long as it is a known thermoplastic resin.

Examples of thermoplastic resins include polyethylene resins, polypropylene resins, vinyl chloride resins, polystyrene resins, acrylonitrile styrene copolymer resins, polyethylene terephthalate resins, acrylic resins, ethylene vinyl acetate copolymer resins, chloride Vinylidene-based resins, polycarbonate-based resins, polyamide-based resins, polyacetal-based resins, polybutylene terephthalate-based resins, fluorine-based resins, thermoplastic elastomers, and the like can be mentioned. These may be used individually by 1 type, and may use 2 or more types together.

The thermoplastic resin that can be used in the present invention is preferably an acrylic resin that requires qualities such as transparency and weather resistance. For example, the second polymer described above may be used.

The acrylic resin layer (Y) may contain various additives as required. Additives include, for example, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, antistatic agents, flame retardants, fillers, matting agents, processing aids, impact resistance aids, antibacterial agents, Antifungal agents, foaming agents, mold release agents, colorants, ultraviolet absorbers, and thermoplastic polymers. These may be used individually by 1 type, and may use 2 or more types together.

When the laminated film is laminated on a substrate for the purpose of protecting the substrate, it is preferable to add an ultraviolet absorber to the acrylic resin layer (Y) to impart weather resistance. The molecular weight of the ultraviolet absorber is preferably 300 or more, more preferably 400 or more. When an ultraviolet absorber having a molecular weight of 300 or more is used, for example, it is possible to prevent mold contamination due to volatilization of the ultraviolet absorber during vacuum molding or pressure molding in an injection mold. In general, the higher the molecular weight of the UV absorber, the less likely it is to bleed out over a long period of time after being processed into a film, and the UV absorber lasts longer than the lower molecular weight.

Furthermore, when the molecular weight of the ultraviolet absorber is 300 or more, the amount of the ultraviolet absorber volatilized is small until the film is produced. Therefore, since the amount of the remaining ultraviolet absorber is sufficient, good performance is exhibited. In addition, the problem that the volatilized ultraviolet absorber recrystallizes and grows over time, adheres to the film, and becomes a defect in appearance is reduced.

As the ultraviolet absorber, a known one can be used, but a benzotriazole-based one having a molecular weight of 400 or more or a triazine-based one having a molecular weight of 400 or more is particularly preferable. Commercially available products of such ultraviolet absorbers include, for example, BASF's trade names Tinuvin 234 and Tinuvin 1577, and ADEKA's trade names Adekastab LA-31 and Adekastab LA-46.

The amount of the ultraviolet absorber to be added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the resin constituting the acrylic resin composition (y), from the viewpoint of weather resistance. , more preferably 1.0 parts by mass or more. From the standpoint of preventing contamination during film formation and the transparency of the molded product, the amount is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.

Moreover, it is preferable to add a light stabilizer to the acrylic resin layer (Y). As the light stabilizer, a known one can be used, but a radical scavenger such as a hindered amine light stabilizer is particularly preferable. Commercially available products of such light stabilizers include, for example, ADEKA's trade name Adekastab LA-57, trade name Adekastab LA-67, trade name Adekastab LA-77, trade name Chimassorb2020FDL and trade name Chimassorb944FDL of BASF Japan. be done.

The amount of the light stabilizer to be added is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the resin constituting the acrylic resin composition (y), from the viewpoint of weather resistance. . From the viewpoint of thermal stability, it is preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less. If it is 2.0 parts by mass or less, the thermal stability during molding can be further improved, the increase in melt viscosity due to thermal deterioration of the resin can be suppressed, and the retention in the molding machine can be reduced, and the thermal deterioration of the resin can be reduced. It is preferable because it can suppress When the molded product obtained is a film, problems such as an increase in defects called fisheyes caused by heat deterioration over time are less likely to occur, and melt extrusion such as film molding can be performed over a long period of time. is.

An antioxidant is preferably added to the acrylic resin layer (Y). As the antioxidant, a known one can be used, but a phenolic antioxidant is particularly preferred. The phenolic antioxidant is not particularly limited, and may be any known phenolic antioxidant that is a compound containing a phenolic hydroxyl group. Commercially available products of such phenol-based antioxidants include, for example, ADEKA's trade names: Adekastab AO-50, trade names: Adekastab AO-60, trade names: Adekastab AO-80; , trade name Irganox 1076.

The amount of the antioxidant to be added is preferably 0.2 parts by mass or more and 0.2 parts by mass or more per 100 parts by mass of the resin constituting the acrylic resin composition (y), from the viewpoint of thermal stability and weather resistance during molding. 5 parts by mass or more is more preferable, and 0.8 parts by mass or more is even more preferable. From the standpoint of preventing contamination during film formation and the transparency of the molded product, the amount is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.

[Method for producing laminated film]
A laminated film can be provided by laminating the film (X) and the acrylic resin layer (Y). As a method for producing the laminated film, a co-extrusion method in which the film (X) and the acrylic resin layer (Y) are melt-extruded and laminated at the same time is preferable because the number of production steps can be reduced.

Methods for laminating a plurality of molten resin layers include (1) a method of laminating molten resin layers before passing through a die, such as a feed block method, and (2) a method of laminating molten resin layers within a die, such as a multi-manifold method. and (3) a method of laminating a molten resin layer after passing through a die such as a multi-slot method.

When the film (X) and the acrylic resin layer (Y) are laminated while being simultaneously melt-extruded, the acrylic resin layer (Y) is melted so as to be in contact with the cooling roll from the standpoint of matting the surface of the fluorine-based film. Extrusion is preferred. Specifically, the laminated film of the present invention can be produced by a production method including the following steps. Two melt extruders are prepared and their cylinder and die temperatures are set at 200-250°C. The resin composition of the film (X) is melt-plasticized in one of the extruders. At the same time, the acrylic resin composition (y) is melt-plasticized in the other extruder. The molten resins extruded from the dies at the ends of both extruders are coextruded onto a cooling roll set at 50 to 100°C.

The film (X) constituting the laminated film and the acrylic resin layer (Y) may each be composed of a plurality of layers.

In the case of melt extrusion, it is preferable to extrude while filtering the resin composition constituting each layer in a molten state with a screen mesh of 200 mesh or more in order to remove nuclei and foreign matter that cause printing defects.

The thickness of the laminated film is preferably 500 µm or less. In the case of a film used for a laminate molded product, the thickness is preferably 30 μm or more, more preferably 50 μm or more. Moreover, 400 micrometers or less are preferable and 300 micrometers or less are more preferable. When the thickness is 30 µm or more, the appearance of the molded article has sufficient depth. Moreover, sufficient thickness can be obtained by stretching, especially when molding into a complicated shape. On the other hand, when the thickness is 400 μm or less, the laminated film has an appropriate rigidity, so lamination properties, secondary workability, etc. are improved. Moreover, it is economically advantageous in terms of mass per unit area. Furthermore, the film formability is stabilized and the production of the film is facilitated.

[Decorative film]
The film (X) and laminated film can be used as decorative films. The decorative film has a pattern layer on at least one side of the film (X) or laminated film. In particular, from the viewpoint of printability, it is preferable to have a pattern layer on the acrylic resin layer.

The pattern layer that constitutes the decorative film can be formed by a known method. In particular, it is preferable to use one or both of the printed layer formed by the printing method and the vapor deposited layer formed by the vapor deposition method as the pattern layer. This printed layer becomes a pattern, characters, or the like on the surface of the laminate obtained by insert or in-mold molding, which will be described later. The printed pattern includes, for example, wood grain, stone grain, cloth grain, sand grain, geometric patterns, letters, all-over solid patterns, metallic patterns, and the like.

Methods for forming the printed layer include known printing methods such as offset printing, gravure rotary printing and screen printing; known coating methods such as roll coating and spray coating; and flexographic printing. The thickness of the printed layer may be appropriately determined as required, and is usually about 0.5 to 30 μm. The thickness of the printed layer may be appropriately selected according to the degree of elongation during molding so that a desired surface appearance can be obtained in a laminate obtained by insert or in-mold molding, which will be described later.

[Laminate molding]
By further laminating the laminated film on the substrate, a laminated molded article having the film (X) on the surface can be produced. Here, the layer is laminated so that the surface on the side of the acrylic resin layer (Y) is in contact with the substrate.

The base material can be appropriately selected according to the intended laminate molded body, and the material thereof includes, for example, resin, wood veneer, wood plywood, particle board, wood board such as medium density fiberboard (MDF), Examples include wood boards such as wood fiber boards, and metals such as iron and aluminum. In the case of resin moldings, thermoplastic resins such as polyvinyl chloride resins, olefin resins, ABS resins, and polycarbonate resins can be used.

The thickness of the base material can be appropriately set as required, and is generally preferably about 20 to 500 μm, more preferably 50 to 300 μm. With the thickness of the substrate, the mechanical properties, handleability, etc. of the film can be maintained.

When the base material has a two-dimensional shape and is made of a heat-sealable material, the base material and the laminated film can be laminated by a method such as thermal lamination. For metal members or the like that are difficult to heat-seal, an adhesive may be used, or one side of the laminated film may be subjected to adhesion processing for lamination. In the case of a three-dimensional laminate, known methods such as an insert molding method, an in-mold molding method, and a three-dimensional overlay laminate molding method can be used.

The three-dimensional overlay laminate molding method refers to the following method. First, two sealed spaces partitioned by a sheet are formed, a compact is placed in one of the spaces, and both spaces or only the space in which the compact is placed is decompressed. Next, the sheet is heated and softened, and in a state in which the molded body is pressed against the sheet surface from one space side to the other space side, only the other space in which the molded body is not arranged is returned to normal pressure, and the difference is The sheet is attached to the compact using pressure.

In the three-dimensional overlay lamination molding method, the heated sheet is applied to the surface of the molded body evenly under pressure, so that the sheet can be adhered to the molded body even if the surface of the molded body is curved. can be attached. As an apparatus for performing three-dimensional overlay lamination molding, for example, "TOM (trade name)" manufactured by Fuse Vacuum Co., Ltd. can be used.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. In the following description, "part" indicates "mass part" and "%" indicates "mass%". Abbreviations indicate the following.
MMA methyl methacrylate BA n-butyl acrylate BDMA 1,3-butylene glycol dimethacrylate AMA allyl methacrylate MA methyl acrylate HEMA 2-hydroxyethyl methacrylate St styrene LPO lauryl peroxide CHP cumene hydroperoxide tBH t-butyl hydroperoxide RS610 mono Sodium n-dodecyloxytetraoxyethylene phosphate
(Phosphanol RS-610NA: manufactured by Toho Chemical Co., Ltd.)
OTP Di-2-ethylhexyl sodium sulfosuccinate
(Pelex OT-P: manufactured by Kao Corporation)
nOM n-octylmercaptan EDTA disodium ethylenediaminetetraacetate SFS sodium formaldehyde sulfoxylate

[Evaluation method]
(1) Average Particle Size of First Polymer The mass average particle size of the first polymer was measured using a LA-910 laser diffraction/scattering particle size distribution analyzer manufactured by HORIBA.

(2) Intrinsic Viscosity of First Polymer The intrinsic viscosity of the first polymer was measured in a chloroform solvent at 25° C. using an AVL-2C automatic viscometer manufactured by Sun Electronics Industry Co., Ltd.

(3) Average particle size of rubber-containing polymer Using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd., the mass average particle size of the rubber-containing polymer was measured by a dynamic light scattering method. .

(4) Gel Content of Rubber-Containing Polymer An acetone solution prepared by dissolving 0.5 g of a rubber-containing polymer as a pre-extraction mass M in 50 mL of acetone is refluxed at 65° C. for 4 hours. The resulting extract is centrifuged at 4° C. and 14,000 rpm for 30 minutes using a high-speed refrigerated centrifuge (manufactured by Hitachi Koki Co., Ltd., trade name: CR21G). The solution is decanted off to give the remaining solid. Refluxing, centrifugation and decantation were repeated for this solid, and the solid obtained was dried at 50° C. for 24 hours. From the mass M before extraction and the mass m after extraction, the gel content G (%) of the rubber-containing polymer was calculated by the following formula.
Gel content G (%) = (mass after extraction m (g)/mass before extraction M (g)) x 100

(5) 60 degree surface glossiness According to JIS Z8741, a portable gloss meter (manufactured by Konica Minolta Co., Ltd., trade name: GM-268Plus) is used to measure the 60 degree surface glossiness of the film (X) side of the laminated film. did. Measurement points were 14 points in total, including 7 points in the width direction of film formation at equal intervals and 2 points in the flow direction of film formation, and all measured values were averaged to obtain a measured value.

(6) Total light transmittance and haze The total light transmittance is measured according to JIS K7361-1, and the haze is measured according to JIS K7136. The total light transmittance and haze of the laminated film were measured under the conditions of a light source of D65 and a temperature of 25°C.

(7) Arithmetic mean roughness (Ra) and mean length of contour elements (Rsm)
Using a surface roughness measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., trade name: SURFCOM 1400D), according to JIS B0601-2001, a measurement length of 4.0 mm, an evaluation length of 4.0 mm, a cutoff wavelength of 0.8 mm, The arithmetic average roughness (Ra) of the film (X) side of the laminated film and the average length (Rsm) of the contour elements were measured at a measurement speed of 0.3 mm/s. In addition, when measuring a long sample such as a film, it can be measured in either the width direction (TD) or the longitudinal direction (MD). There is
The arithmetic mean roughness (Ra) is obtained by extracting only the reference length from the roughness curve in the direction of the average line, taking the X axis in the direction of the average line of this extracted part, and the Y axis in the direction of the longitudinal magnification. , when the roughness curve is represented by y=f(x), the value obtained by the following formula is expressed in micrometers (μm).

The mean length (Rsm) of the profile element is the average of the length Xs of the profile element in the reference length, and is the value obtained by the following formula expressed in micrometers (μm). Also, Xsi is the length for one profile curve element.

(8) Chemical resistance evaluation 1
Gauze is placed on the surface of the film (X) side of the laminated film (test piece), one drop of suntan lotion (trade name: Coppertone Waterbabies SPF50) is dropped on it, and a 5 cm × 5 cm aluminum plate is placed on it. and a load of 500 g were placed in this order and left at 74° C. for 1 hour. Next, the test piece was washed with a neutral detergent and air-dried, and the surface of the test piece was visually observed to evaluate the chemical resistance according to the following criteria.
◯: No change on the surface of the test piece.
Δ: Slight traces of the solvent remain on the surface of the test piece.
x: Clear traces of the solvent or gauze remain on the surface of the test piece, or the surface in contact with the solvent becomes cloudy.

(9) Chemical resistance evaluation 2
One drop of 10% lactic acid aqueous solution was dropped on the surface of the laminated film (test piece) on the film (X) side, and left at 80° C. for 24 hours. Next, the test piece was washed with a neutral detergent and air-dried, and the surface of the test piece was visually observed to evaluate the chemical resistance according to the following criteria.
◯: No change on the surface of the test piece.
Δ: Slight traces of the solvent remain on the surface of the test piece.
x: Clear traces of the solvent remain on the surface of the test piece, the film surface is swollen, or the surface in contact with the solvent becomes cloudy.

(10) Number of fisheyes in film Visually observe the number of fisheyes with a size of 0.05 mm ² or more in film (X) having a thickness of 40 μm using a table for measuring impurities (manufactured by Choyokai Co., Ltd.). did. The number of fisheyes was calculated by measuring 5 sheets of the film cut in the range of 0.01 m ² and averaging the total number of measurements.

(Production Example 1: Production of hydroxyl group-containing polymer (1))
A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, etc., was charged with the following monomer mixture (1). Then, after the inside of the vessel was sufficiently replaced with nitrogen gas, the monomer mixture (1) in the reaction vessel was heated to 75° C. with stirring and reacted for 3 hours in a nitrogen gas stream. After that, the temperature in the reaction vessel was raised to 90° C. and maintained at 90° C. for 45 minutes to complete the polymerization. to obtain a hydroxyl group-containing polymer (1).
The obtained hydroxyl group-containing polymer (1) had a glass transition temperature of 77° C., an intrinsic viscosity of 0.11 L/g, an Mw/Mn of 2.1, and an average particle size of 70 μm.

<Monomer mixture (1)>
MA: 10 parts MMA: 60 parts HEMA: 30 parts nOM: 0.18 parts LPO: 1 part Tribasic calcium phosphate: 1.8 parts Deionized water: 250 parts

(Production Example 2: Production of rubber-containing polymer (2-1))
After 195 parts of deionized water was added to a polymerization vessel equipped with a stirrer, condenser, thermocouple, and nitrogen inlet tube, 0.3 parts of MMA, 4.5 parts of BA, 0.05 parts of AMA, 0.2 parts of BDMA, and 0 CHP were added. A premix of 0.025 part and 1.3 part of RS610 was added, and the temperature was raised to 75°C. After raising the temperature, a mixture of 5 parts of deionized water, 0.20 parts of SFS, 0.0001 parts of ferrous sulfate and 0.0003 parts of EDTA was charged into the polymerization vessel at once to initiate polymerization. After confirming the temperature rise peak, the temperature was maintained for 15 minutes to complete the polymerization of the first elastic polymer (S-1-1).
Subsequently, 9.6 parts of MMA, 14.4 parts of BA, 0.25 parts of AMA, 1.0 part of BDMA and 0.016 parts of CHP were dropped into the polymerization vessel over 90 minutes. After that, the mixture was held for 60 minutes to complete the polymerization of the second elastic polymer (S-2-1).
The Tg of the first elastic polymer (S-1-1) was -48°C, and the Tg of the second elastic polymer (S-2-1) was -10°C.

Subsequently, 6.0 parts of MMA, 4.0 parts of BA, 0.075 parts of AMA and 0.0125 parts of CHP were dropped into the polymerization vessel over 45 minutes. After that, the mixture was held for 60 minutes to complete the polymerization of the intermediate polymer (M-1). The Tg of the intermediate polymer (M-1) was 60°C.

Finally, 57.0 parts of MMA, 3.0 parts of MA, 0.075 parts of tBH and 0.264 parts of nOM were dropped into the polymerization vessel over 140 minutes. After that, it was held for 60 minutes to complete the polymerization of the hard polymer (H-1). The Tg of the hard polymer (H-1) was 79.3°C.
The average particle size of the obtained latex-like rubber-containing polymer (2-1) was 0.11 μm.

100 parts of the latex-like rubber-containing polymer (2-1) was filtered by a vibrating filter equipped with a SUS mesh having an opening of 62 μm. Then, the latex was coagulated by dropping into 100 parts of hot water at 80° C. containing 3.5 parts of calcium acetate. Further, the temperature was raised to 95° C. and held for 5 minutes to solidify. The resulting coagulate was separated, washed and dried at 75° C. for 24 hours to obtain a powdery rubber-containing polymer (2-1). The rubber-containing polymer (2-1) had a gel content of 70% and an Mw of 58,000.

(Production Example 3: Production of rubber-containing polymer (2-2))
A rubber-containing polymer (2-2) was produced by the following method by changing the ratio of each raw material to the ratio shown in Table 1.
244 parts of deionized water was placed in a polymerization vessel equipped with a reflux condenser, and the temperature was raised to 80°C. Next, a mixed aqueous solution of 0.6 parts of SFS, 0.00012 parts of ferrous sulfate and 0.0003 parts of EDTA was added to the polymerization vessel, and while stirring under a nitrogen atmosphere, the first-stage monomer mixture was 1/15 was charged and held for 15 minutes.
Next, the remaining first-stage monomer mixture was added dropwise so that the rate of increase with respect to water was 8%/hour, and the mixture was held for 60 minutes to obtain a polymer latex. The Tg of the polymer obtained from the first-stage monomer mixture was 4°C.

0.6 part of SFS was added to the polymer latex and held for 15 minutes. Then, while stirring at 80 ° C. under a nitrogen atmosphere, the second-stage monomer mixture was added dropwise so that the rate of increase with respect to water was 4% / hour, and then held for 120 minutes to obtain a polymer latex. got The Tg of the polymer obtained from the second-stage monomer mixture was -37°C.

0.4 part of SFS was added to the polymer latex and held for 15 minutes. Then, under a nitrogen atmosphere, while stirring at 80° C., the monomer mixture of the hard polymer was added dropwise so that the rate of increase with respect to water was 10%/hour, and then held for 60 minutes to obtain the rubber-containing polymer ( 2-2) was obtained. Incidentally, the Tg of the hard polymer was 99°C.

The obtained latex rubber-containing polymer (2-2) had an average particle size of 0.28 μm.
100 parts of the latex-like rubber-containing polymer (2-2) was filtered by a vibrating filter equipped with a SUS mesh having an opening of 150 μm. Then, it was salted out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water to recover the solid content, and dried to obtain a powdery rubber-containing polymer (2-2). The resulting rubber-containing polymer (2-2) had a gel content of 90% and an Mw of 45,000.

(Production Example 4: Production of acrylic resin composition (y))
80 parts of the rubber-containing polymer (2-1) obtained in Production Example 2, 10 parts of the rubber-containing polymer (2-2) obtained in Production Example 3, an acrylic resin (Mitsubishi Chemical Co., Ltd. 10 parts of Acrypet MD), 1.4 parts of UV absorber (manufactured by BASF Japan Co., Ltd., trade name: Tinuvin 234) as an additive, light stabilizer (ADEKA Co., Ltd., product 0.3 part of LA-57) and 0.1 part of an antioxidant (manufactured by BASF Japan Ltd., trade name: Irganox 1076) were added and then mixed using a Henschel mixer.

This mixture is degassed extruder (manufactured by Toshiba Machine Co., Ltd., trade name: TEM-35B, hereinafter the same) using a cylinder temperature of 100 to 240 ° C. and a die temperature of 240 ° C. to remove impurities with a screen mesh. The strands were extruded while being removed, passed through a water tank, cooled, and then cut to obtain pellets of the acrylic resin composition (y).

(Production Example 5: Production of second polymer (1))
A second copolymer (1) was obtained according to the method for producing a hard (co)polymer (B-1) in Production Example 7 of JP-A-2003-313392.

(Production Example 6: Production of the third polymer (1))
A third polymer (1) was obtained according to the method for producing the copolymer composition (b-2) of Reference Example 2 of JP-A-2000-319516.

(Production Example 7: Production of fourth polymer (1))
A fourth polymer (1) was obtained according to the method for producing a thermoplastic polymer (VII-1) disclosed in JP-A-2005-139416.

[Example 1]
A multi-manifold die was installed at the tip of the 40 mmφ single-screw extruder 1 and the 30 mmφ single-screw extruder 2 .
Pellets of the acrylic resin composition (y) obtained in Production Example 4 were supplied to a single-screw extruder 1 having a cylinder temperature of 230 to 240° C. and melt-plasticized.

Separately, 68 parts of PVDF (manufactured by Kureha Co., Ltd., trade name KFT #850) as a fluorine-based resin, 9 parts of a hydroxyl group-containing polymer (1) as a first polymer (1), and a second 18 parts of the polymer (1), 0.8 parts of the third polymer (1) (Mw = 160000), 5 parts of the fourth polymer (1) (Mw = 1500000), an antioxidant (( ADEKA Co., Ltd., trade name: ADEKA STAB AO-60) was mixed with 0.8 parts.
This mixture is extruded into strands using a degassing extruder at a cylinder temperature of 100 to 240 ° C. and a die temperature of 250 ° C. while removing impurities with a screen mesh, cooled through a water tank, cut and pelletized. did. The pellets were supplied to a single-screw extruder with a cylinder temperature of 200-230° C. and melt-plasticized.

These molten plasticized materials were supplied to a multi-manifold die heated to 240° C. to obtain a laminated film having a film (X) layer with a thickness of 8.7 μm and an acrylic resin layer (Y) with a thickness of 66.3 μm. rice field.
At that time, the temperature of the cooling roll was set to 80° C., and the laminated film was obtained in such a manner that the acrylic resin layer (Y) was in contact with the cooling roll. Table 2 shows the evaluation results of the obtained laminated film.

[Example 2]
A laminated film of 75 μm was obtained in the same manner as in Example 1, except that the formulation was changed to that shown in Table 2. Table 2 shows the evaluation results of the obtained laminated film.

[Comparative Example 1]
A laminated film of 75 μm was obtained in the same manner as in Example 1, except that the formulation was changed to that shown in Table 2. Table 2 shows the evaluation results of the obtained laminated film.

[Comparative Example 2]
A laminated film of 75 μm was obtained in the same manner as in Example 1, except that the formulation was changed to that shown in Table 2. Table 2 shows the evaluation results of the obtained laminated film.

The above examples and comparative examples have revealed the following.
The films obtained in Examples 1 and 2 had an arithmetic mean roughness Ra of 0.1 to 1.0 μm, an average contour element length Rsm of 30 to 100 μm, and had a matte appearance with a glittery appearance. It was extremely low, and the design and decoration properties, such as a sense of luxury and depth, were good. It also has excellent chemical resistance to sunscreen and 10% lactic acid. Furthermore, the number of fish eyes with a size of 0.05 mm ² or more was 20/0.01 m ² or less, and the appearance was excellent with very few defects. By adding two or more types of specific acrylic polymers, it is possible to impart lubricity and long-running properties to the resin composition, which prevents heat deterioration of the resin during extrusion and adhesion of degraded resin at the die exit. can be prevented and the occurrence of fish eyes can be reduced.
On the other hand, the films obtained in Comparative Examples 1 and 2 had good matting properties and chemical resistance, but the number of fisheyes with a size of 0.05 mm ² or more was 20/0.01 m ² or less. , inferior in appearance due to many defects. Therefore, it is difficult to develop applications that require quality, and for example, when a printed layer is applied directly or after lamination on a resin sheet, there is a possibility that problems such as ink loss will frequently occur.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can reduce fisheyes that cause film appearance defects, and is excellent in fine matting properties, transparency, and chemical resistance.

As described above, the matte film, laminated film, decorative film, laminated sheet and laminated molded product produced from the resin composition of the present invention are particularly suitable for vehicle applications and building material applications. Specific examples include instrument panels, console boxes, meter covers, door lock pedals, steering wheels, power window switch bases, center clusters, automotive interior applications such as dashboards, weather strips, bumpers, bumper guards, side mudguards, body panels, Spoilers, front grilles, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, head lamp covers, tail lamp covers, windshield parts, etc. Automobile exterior applications, AV equipment and furniture products Applications such as front panels, buttons, emblems, surface decorative materials, etc., applications such as mobile phone housings, display windows, buttons, etc., exterior materials for furniture, interior materials for construction such as walls, ceilings, floors, etc. External walls such as siding, fences, roofs, gates, gable boards, and other building exterior materials; surface decorative materials for furniture such as window frames, doors, handrails, thresholds, and lintels; various displays, lenses, mirrors, goggles, Optical member applications such as window glass, interior and exterior applications for various vehicles other than automobiles such as trains, aircraft, and ships, various packaging containers and materials such as bottles, cosmetic containers, and accessory cases, miscellaneous goods such as prizes and small items, etc. It can be suitably used for various uses.

Claims (13)

A resin composition containing a fluororesin, a first polymer, a second polymer, and a third polymer,
The first polymer is a polymer having a reactive group,
The second polymer has, as a structural unit, a (meth)acrylic acid alkyl ester having 1 or more and 3 or less carbon atoms in the ester group, and has substantially no reactive group. is a coalescence,
The third polymer is a polymer containing 30% by mass or more of a (meth)acrylic acid alkyl ester having an ester group having 4 or more carbon atoms as a structural unit and substantially having no reactive group. can be,
A resin composition in which the composition of the second polymer and the composition of the third polymer are different. 2. The resin composition according to claim 1, wherein the third polymer has a mass average molecular weight of 50,000 to 500,000. Further, it has a methacrylic acid alkyl ester having an ester group with a carbon number of 1 to 3 and a (meth)acrylic acid alkyl ester having an ester group with a carbon number of 4 to 18 as structural units, and is substantially reactive 3. The resin composition according to claim 1, which contains a fourth polymer having no groups. The resin composition according to any one of claims 1 to 3, wherein the fourth polymer has a mass average molecular weight of 500,000 or more and 5,000,000 or less. The ratio of the fluororesin to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 40% by mass or more and 98% by mass or less. , The resin composition according to any one of claims 1 to 4. The ratio of the first polymer to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 1% by mass or more and 20% by mass. The resin composition according to any one of claims 1 to 5, wherein: The ratio of the second polymer to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 1% by mass or more and 40% by mass. The resin composition according to any one of claims 1 to 6, wherein: The ratio of the third polymer to the total 100% by mass of the fluororesin, the first polymer, the second polymer, and the third polymer is 0.1% by mass or more 10 % by mass or less, the resin composition according to any one of claims 1 to 7. The resin composition according to any one of claims 1 to 8, wherein the fluororesin is polyvinylidene fluoride. The resin composition according to any one of claims 1 to 9, wherein the first polymer is an acrylic polymer. One or more selected from the group consisting of reactive groups, carboxy groups, hydroxy groups, acid anhydride groups, epoxy groups, isocyanate groups, amide groups, amino groups, cyano groups and imine groups possessed by the first polymer The resin composition according to any one of claims 1 to 10. A film comprising the resin composition according to any one of claims 1 to 11. A molded article comprising the film according to claim 12 .