JPH04202280A - Colored laminated film based on vinylidene fluoride and laminate made by using it - Google Patents

Abstract

PURPOSE:To make it possible to effect lamination at low temperature on a base material by laminating a hot-melt adhesive layer comprising an ethylene/ ethyl acrylate resin on a specified vinylidene fluoride resin layer. CONSTITUTION:100 pts.wt. vinylidene fluoride polymer is mixed with 7-60 pts.wt. polymethyl methacrylate resin containing 0-50wt.% other acrylic resin and 7-60 pts.wt. pigment preferably comprising an inorganic pigment, and the mixture is pelletized and then extruded in film form to give a vinylidene fluoride resin layer (A) having a thickness of at least 10mum. An ethylene/ethyl acrylate resin having an ethyl acrylate comonomer content of 25-40wt.% and an MI (ASTM D1238) of 4-250g/10min is extruded to form a film, giving a hot-melt adhesive layer (B) 10-30mum in thickness. Component B is laminated on component A.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a vinylidene fluoride-based colored laminated film that can be laminated at low temperatures on various resin molded bodies in the form of films or plates, and paper, and a colored laminated film using the same. Regarding a laminate.

[Conventional technology]

Polyvinylidene fluoride has weather resistance, chemical resistance, water resistance,
Due to its excellent stain resistance, it has traditionally been used as an exterior wall coating material and as a lining material for chemical tanks. Also,
Films processed from vinylidene fluoride resins such as polyvinylidene fluoride can be used as protective films to prevent surface contamination or deterioration of physical properties of base materials such as steel plates, polyvinyl chloride plates, ABS resin plates, and precast concrete plates. has been done. This type of film has an adhesive layer formed on the surface to be adhered to the above-mentioned base material. Furthermore, as this type of film, a colored film has been developed in which a pigment is mixed into a raw resin to prevent the base material from being photodegraded or discolored.

Such vinylidene fluoride resin films generally have low wettability with adhesives and have poor adhesion to adhesives.

Therefore, in order to form an adhesive layer on a vinylidene fluoride resin film, it is necessary to mix polymethyl methacrylate resin, which has good compatibility with the vinylidene fluoride resin, into the raw material resin of the film, or to form an adhesive layer on the film. It is necessary to improve the adhesion and wettability of the film surface with the adhesive in advance by subjecting the surface on which the film will be formed to a surface treatment. Generally, adhesion is increased by mixing polymethyl methacrylate resin. Conventionally, polymethyl methacrylate has been used as the raw material resin for the adhesive layer.

Other examples include epoxy resin, polyurethane, and polyester, which can also provide sufficient adhesive strength, but are inferior to polymethyl methacrylate in terms of weather resistance.

[Problem to be solved by the invention]

However, when laminating a laminated film having an adhesive layer made of polymethyl methacrylate to a base material, since the melting point of polymethyl methacrylate is relatively high, a temperature of at least 150°C or higher is required to obtain sufficient adhesive strength. It was necessary to crimp it with For this reason, when the above laminated film is laminated onto a base material made of a thermoplastic resin with a relatively low softening temperature, such as polyvinyl chloride, using a hot roll or press at a temperature of 150°C or higher, the base resin will Heat may cause deformation or discoloration. Additionally, the melting point of the vinylidene fluoride resin film itself that is laminated is almost the same as that of the polymethyl methacrylate adhesive layer, so the vinylidene fluoride resin film itself could deteriorate under the influence of heat during lamination. .

[Means to solve the problem]

The purpose of the present invention is to sufficiently protect a base material by taking advantage of the excellent weather resistance, chemical resistance, water resistance, stain resistance, etc. of vinylidene fluoride resin, and to prevent photodeterioration and discoloration of the base material. For colored films that can be laminated, even if the base material to be laminated is a resin with a low softening temperature or melting point, it can be laminated at a low enough temperature that there is no fear of deformation or discoloration of the base material or thermal deterioration of the vinylidene fluoride resin layer. An object of the present invention is to provide a colored vinylidene fluoride laminated film and a laminate using the same.

That is, the present invention achieves the above object by: (a) 100 parts by weight of a vinylidene fluoride polymer, 7 to 60 parts by weight of a polymethyl methacrylate resin, and 7 parts by weight of a pigment.
A colored vinylidene fluoride laminated film is provided, in which a hot melt adhesive layer made of (b) ethylene ethyl acrylate resin is laminated on a vinylidene fluoride resin layer containing -60 parts by weight.

The present invention also provides a laminate obtained by laminating the above-mentioned vinylidene fluoride colored laminate film onto a thermoplastic resin or paper.

(a) Vinylidene fluoride resin layer (a) The vinylidene fluoride resin layer is a layer containing a polymethyl methacrylate resin and a pigment in addition to the vinylidene fluoride polymer as the main component.

The vinylidene fluoride polymer used in the present invention includes not only vinylidene fluoride homopolymers (polyvinylidene fluoride) but also vinylidene fluoride as a main component as long as the excellent properties of the vinylidene fluoride resin are not impaired. It may also be a copolymer with other comonomers.

Preferred comonomers include, for example, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl fluoride, and the like.

This vinylidene fluoride resin layer has low wettability and compatibility with vinylidene fluoride polymer as the main component alone.
It is difficult to bond with other resins.

For this reason, this vinylidene fluoride resin layer is mixed with a polymethyl methacrylate resin that has good compatibility with the vinylidene fluoride polymer, thereby improving adhesiveness.

The polymethyl methacrylate resin to be added is as follows:
Examples include polymethyl methacrylate and mixtures of polymethyl methacrylate and other acrylic resins.

Examples of acrylic resins that can be mixed with polymethyl methacrylate include homopolymers such as polymethyl acrylate, polyethyl acrylate, polyethyl methacrylate, and polybutyl methacrylate, ethylene-acrylic ester copolymers, and styrene. - Acrylic ester-acrylic acid copolymer, styrene-methacrylic ester-acrylic acid copolymer, acrylic ester-vinyl chloride copolymer, styrene-methacrylic ester-butadiene copolymer, methacrylic ester-butadiene copolymer Examples include polymers, methacrylic acid ester-acrylonitrile copolymers, and the like. These can be used singly or in combination of two or more. The content ratio of these acrylic resins in polymethyl methacrylate resin is
It is usually 0 to 50% by weight, preferably 5 to 30% by weight.

The polymethyl methacrylate resin is added in an amount that does not impair physical properties such as weather resistance, chemical resistance, stain resistance, and mechanical strength of the vinylidene fluoride resin layer. The specific amount added is vinylidene fluoride polymer 100
Per part by weight, polymethyl methacrylate resin 7-6
It is necessary that the amount is 0 parts by weight, preferably 7 to 25 parts by weight.
Parts by weight.

Furthermore, since the vinylidene fluoride resin layer has high ultraviolet transmittance if only the vinylidene fluoride polymer and the polymethyl methacrylate resin are used, pigments are added and colored to suppress this.

Due to this coloring, the vinylidene fluoride resin layer has an enhanced ultraviolet blocking effect, so that it is possible to prevent photodeterioration and discoloration of the base material to be laminated.

The pigment to be added is not particularly limited, but preferably an inorganic pigment that has good weather resistance and does not change color. Examples of such inorganic pigments include inorganic oxide pigments such as TiO2, and N1 (hsb20s solid solution, NiFe2O4-NiC
r2O4 solid solution, CozTiOi-NizTiOn-Z
Examples include n2Ti04 solid solution and inorganic composite oxide pigments such as C0Al2O4. These can be used singly or in combination of two or more.

The amount of these pigments added to the vinylidene fluoride resin layer is 7 parts by weight per 100 parts by weight of the vinylidene fluoride polymer.
~60 parts by weight, preferably 1
The amount is 5 to 40 parts by weight.

When forming this vinylidene fluoride resin layer, for example, a vinylidene fluoride polymer, a polymethyl methacrylate resin, and a pigment are kneaded using a twin screw extruder, pelletized, and then pelletized using a single screw extruder. It is formed by extruding it into a film using a T-die.

The vinylidene fluoride resin layer formed in this way preferably has a thickness of at least 10 μm, particularly preferably a thickness of at least 10 μm, in order to ensure sufficient weather resistance, ultraviolet blocking properties, physical strength, etc. as a protective layer. is 15 to 25 μm.

(b) Hot melt adhesive layer (b) Hot melt adhesive layer is a layer containing ethylene ethyl acrylate resin as a main component.

The ethylene ethyl acrylate resin used in the present invention is an ethylene-ethyl acrylate copolymer, and preferably has an ethyl acrylate comonomer content of 25 to
It is 40% by weight. If the content of ethyl acrylate comonomer is less than 25% by weight, the adhesive strength will be poor;
If it exceeds 5% by weight, the strength as an adhesive will be poor, which is not preferable. Furthermore, the melt index of the ethylene ethyl acrylate resin used in the present invention is 4 to 250 g.
/l10m1n (measured according to the method specified in AST D-1238).

When forming this hot melt adhesive layer, for example, the above-mentioned ethylene ethyl acrylate resin is formed into a film-like hot melt adhesive by extrusion film molding.

This hot melt adhesive layer is formed to a thickness that provides sufficient adhesive strength. The specific thickness is usually 10~
The thickness is about 30 μm, preferably 15 to 25 μm.

This hot melt adhesive layer can be formed without using organic solvents, so it is easy to handle, has sufficient adhesion to the vinylidene fluoride resin layer, and has weather resistance, water resistance, etc. It has excellent physical properties. Further, the ethylene ethyl acrylate resin used in the present invention is characterized by a softening temperature of 80° C. or lower, and has excellent low-temperature adhesive properties as a hot melt adhesive. Therefore, even when the colored laminated film of the present invention is thermally laminated to a thermoplastic resin with a low softening temperature, such as polyvinyl chloride, polyethylene, or polypropylene, the temperature must be maintained at a temperature that does not cause deformation or thermal deterioration of these thermoplastic resins. It is possible to laminate. For example, it has been found that most thermoplastic resins do not deteriorate due to heat if the lamination temperature is kept below 120°C. Since the colored laminated film of the present invention can be laminated even at a temperature of about 100°C, it can be laminated even on a base material made of a thin film-like thermoplastic resin without causing thermal deterioration. Furthermore, since ethylene ethyl acrylate resin is flexible even at low temperatures, it retains its flexibility even when laminated onto a film such as polyvinyl chloride.

Note that this hot melt adhesive layer can be obtained using only ethylene ethyl acrylate resin as a raw material, but in order to improve adhesiveness, it is preferable to add or blend a tackifier or the like to the raw resin. Examples of the tackifier to be added include rosin derivatives, terpene resins, styrene and styrene copolymers, phenolic resins, polyethylene, and ethylene-vinyl acetate copolymers. These can be used singly or in combination of two or more.

The content ratio of these tackifying agents in the hot melt adhesive layer is usually 0 to 50 parts by weight, preferably 10 to 4 parts by weight, per 100 parts by weight of ethylene ethyl acrylate resin.
It is 0 parts by weight.

Furthermore, an ultraviolet absorbing material such as tinuvin can be added to this hot melt adhesive layer, thereby increasing the ultraviolet blocking effect.

Method for Producing Colored Laminated Film The colored laminated film of the present invention is obtained by laminating the hot melt adhesive layer on the vinylidene fluoride resin layer. Examples of methods for laminating these layers include the following two methods.

The first method is to mix vinylidene fluoride polymer, polymethyl methacrylate resin, and pigment into pellets using a twin-screw extruder, and then pelletize the vinylidene fluoride resin pellets using a single-screw extruder. The ethylene ethyl acrylate resin is extruded into a film using a die, then the ethylene ethyl acrylate resin is formed into a film using a single screw extruder using a T-die, and the still molten film ethylene ethyl acrylate resin is transferred to a laminating device. This is a method of laminating the above-mentioned film-like vinylidene fluoride resin using the following method.

The second method is to form both a vinylidene fluoride resin and an ethylene ethyl acrylate resin into a film, and then laminate the two types of film resins using a hot roll.

Laminate The laminate of the present invention is produced by laminating the colored laminate film of the present invention on the surface of a target substrate.

Target substrates include various film- or plate-shaped resin moldings made of resins such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyamide, polyester, polyvinylidene chloride, polyvinyl alcohol, and polyacetal, and paper. . In this way, even if the target substrate is a resin with a low softening temperature or melting point, if the colored laminated film of the present invention is used, the substrate resin will not be thermally degraded during lamination.

According to such a laminate, the colored laminate film of the present invention acts as a protective film with excellent weather resistance, chemical resistance, stain resistance, and water resistance, so that the life of the base material can be significantly extended. can. Specifically, the colored laminated film in this laminate has traditionally been used as a surface protection film for polyvinyl chloride corrugated plates used in arcades, etc., or polyvinyl chloride film for vinyl houses. By improving the weather resistance of
This greatly extends its lifespan. In addition, the colored laminated film of the present invention is resistant to organic solvents and is resistant to stains, so it can be used for wallpaper, etc. on areas that are prone to oil stains, such as kitchen walls, and areas that are prone to cigarette grease. In that case, the chemical resistance and stain resistance of wallpaper etc. are improved, and its lifespan can be significantly extended.

〔Example〕

Example 1 Polyvinylidene fluoride (“Solef 100” manufactured by Tsurubay Co., Ltd.
8), methyl methacrylate resin, and pigment were mixed using a twin screw extruder at a ratio of 60 parts by weight: 10 parts by weight = 30 parts by weight, and pelletized. This pellet was extruded with a 40mm extruder using a 400mm 1l@T die, and
This was processed into a 0M wide film to produce a 20 μm thick uniform colored film. As the methyl methacrylate resin, Acryvet MDJ manufactured by Mitsubishi Rayon Co., Ltd. was used.The pigment was TiO2.

Next, ethylene ethyl acrylate resin [rGB301J manufactured by Nippon Unicar Co., Ltd., containing 35% by weight of ethyl acrylate, melt index 4 g/110 m1n (AST
D-1238)], 440mm
It was extruded into a film using a 400 mmtt@T-die to form a hot melt film that would become a hot melt adhesive layer. At this time, while melting and extruding the hot melt film, the colored film made of polyvinylidene fluoride resin, which had been formed into a film in advance, was laminated using a laminating machine at 80°C and 5 kgf/al to form a colored laminated film. was formed. This colored laminated film was placed on a polyvinyl chloride board (base material) at 80°C for 2 hours.
Press lamination was performed under the conditions of 0 kgf/car for 5 minutes, and this was used as a test piece.

Regarding this test piece, the state of the base material was evaluated by the following evaluation method, and the weather resistance, water resistance, adhesiveness, and chemical resistance were evaluated by the following tests.

Evaluation of the state of the base material: The state of the base resin was observed after lamination with the protective film. In Table 1, cases where there was no effect at all are shown as ○, and cases where the base resin deteriorated are shown as x.

Weather resistance test: 200 by sunshine weather meter accelerated exposure test
Changes after 0 hours were examined. In Table 1, those with no change are shown as ○, those that were slightly affected are shown as △, and those that were peeled from the colored laminated film or substrate are shown as ×.

Water resistance test: After immersing the test piece in 25°C water for 72 hours, JIS
A 180 degree angle peel test was conducted according to K6854. 1st
The table shows the adhesive strength. Also, those that peeled off during the test are indicated as x.

Adhesion test: After producing the test piece, it was left in the air at room temperature for 24 hours, and then a 180 degree peel test was conducted in accordance with JIS K 6854. The results are shown in Table 1.

Chemical resistance test: Soak the test piece in 30% HC1, 20% NaOH, THF, methyl ethyl ketone (MEK), ) luene for 24 hours.
Observed after an hour. In Table 2, items with no change are shown as ○, and items that were slightly affected are shown as △.

Example 2 A colored film serving as a polyvinylidene fluoride resin layer of a colored laminated film was produced in the same manner as in Example 1. next,
Ethylene ethyl acrylate resin (manufactured by Nippon Unicar Co., Ltd.)
GB301J) to 400mm1@T using a 40mm extruder.
- It was molded into a film using a die to form a hot melt film that would become a hot melt adhesive layer. At this time,
While extruding the hot melt film, the colored film made of polyvinylidene fluoride resin, which had been formed in advance, was heated at 80°C using a laminating machine.
A colored laminated film was formed by laminating at 5 kgf/aIF. This colored laminated film was placed on a polycarbonate plate at 80°C and 20kgf/co? , Press lamination was performed for 5 minutes, and this was used as a test piece. This test piece was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 3 A colored laminated film was produced in the same manner as in Example 1. This colored laminated film was heat roll laminated onto a 50 μm thick polyvinyl chloride film at 80° C., 5 kgf/ci, and 1 m/sec, and this was used as a test piece.

This test piece was evaluated in the same manner as in Example 1.

The results are shown in Tables 1 and 2.

Comparative Example 1 Ethylene ethyl acrylate resin was not used as a hot melt adhesive, and instead, polymethyl methacrylate adhesive was applied to a colored film made of polyvinylidene fluoride resin produced in the same manner as in Example 1. A laminated film was produced. After drying, this colored laminated film was placed on a polyvinyl chloride plate at 80°C, 20kgf/Ci,
Press lamination was performed for 5 minutes, and this was used as a test piece. This test piece was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Comparative Example 2 A colored laminated film produced in the same manner as [Comparative Example] was placed on a polyvinyl chloride board at 160°C, 20 kgf/aIr, 5
It was press laminated under the conditions of 1 minute to obtain a test piece.

This test piece was evaluated in the same manner as in Example 1.

The results are shown in Tables 1 and 2.

In Comparative Example 2, the polyvinyl chloride (base resin) was deformed because it was laminated at a high temperature exceeding 150°C, and the polyvinylidene fluoride resin film also deteriorated due to the heat. Therefore, tests for weather resistance, water resistance, adhesion, and chemical resistance have not been conducted.

Comparative Example 3 Colored laminated film 50 produced in the same manner as Comparative Example 1
15kg at 160°C on μmW polyvinyl chloride film
f/co? , 1 m/sec to prepare a test piece. This test piece was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

In Comparative Example 3, the polyvinyl chloride (base resin) melted because it was laminated at a high temperature exceeding 150°C. Therefore, tests of weather resistance, water resistance, adhesion, and chemical resistance could not be conducted.

Comparative Example 4 The procedure was the same as in Example 1, except that the mixing ratio of polyvinylidene fluoride, methyl methacrylate resin, and pigment during production of the colored film was changed to 30 parts by weight: 40 parts by weight: 30 parts by weight. A test piece was prepared. This test piece was evaluated in the same manner as in Example j. The results are shown in Tables 1 and 2.

Table 1 Table 2 (Chemical resistance) [Effects of the invention] Since the vinylidene fluoride colored laminated film of the present invention has a vinylidene fluoride resin layer, it has weather resistance, water resistance,
In addition to having excellent chemical resistance, the vinylidene fluoride resin layer is colored, so it is possible to prevent photodeterioration and discoloration of the thermoplastic resin such as polyvinyl chloride that serves as the base material. In addition, since the hot melt adhesive layer laminated on one side of the vinylidene fluoride resin layer is made of ethylene ethyl acrylate resin, it has good adhesion at low temperatures and has a
Bonding is possible even at a relatively low temperature of 00°C. For this reason, this vinylidene fluoride-based colored laminated film can be easily heat-laminated without thermal deformation or loss of physical properties of the base material, and is difficult to peel off, so it can be used on the surface of thermoplastic resins with a low softening point. Particularly suitable as a protective film. Specifically, it is suitable as a surface protection film for polyvinyl chloride corrugated plates used in arcades, etc., polyvinyl chloride film for vinyl houses, and as a surface protection film for base resins. When used, it has excellent effects such as improving weather resistance and significantly extending life. Furthermore, this colored laminated film can be laminated onto base materials other than resins, and for example, by taking advantage of its water resistance and chemical resistance, it can be used as a stain prevention film for wallpaper and the like.

Agent: Patent attorney Shushi Iwamiya

Claims (2)

[Claims] (1) (a) 100 parts by weight of vinylidene fluoride polymer,
(b) A hot melt adhesive layer made of ethylene ethyl acrylate resin is laminated on a vinylidene fluoride resin layer containing 7 to 60 parts by weight of a polymethyl methacrylate resin and 7 to 60 parts by weight of a pigment. Vinylidene chloride colored laminated film. (2) A laminate obtained by laminating the vinylidene fluoride colored laminate film according to claim 1 on a thermoplastic resin or paper.