JP2008265062A - Acrylic resin film for thermoforming, its manufacturing method, and laminate containing the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an acrylic resin film for thermoforming, which is equipped with an excellent chemical resistance, scratch resistance, surface hardness and heat resistance, and a laminate containing the acrylic resin film. <P>SOLUTION: In this acrylic resin film for thermoforming, surface glossiness at an angle of 60° is 100% or more, and a cured resin layer with a thickness of 2-12 μm is provided as the outermost layer on one surface of an acrylic resin film. The laminate contains the acrylic resin film for thermoforming. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention includes a laminate having particularly excellent chemical resistance, specifically, a novel thermoforming acrylic resin film having both chemical resistance and mechanical strength, a method for producing the same, and the thermoforming acrylic resin film. It relates to a laminate.

  There are an insert molding method and an in-mold molding method as methods for imparting design properties to a molded product at low cost. In the insert molding method, a film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated by printing or the like is previously formed into a three-dimensional shape by vacuum forming or the like, and an unnecessary film or sheet portion is removed. Then, it is transferred into an injection mold, and a molded product integrated by injection molding of a resin as a base material is obtained. On the other hand, the in-mold molding method is a method in which a film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated for printing or the like is placed in an injection mold, subjected to vacuum molding, and then in the same mold. In this way, an integrated molded product is obtained by injection molding a resin as a base material.

As a molded product using an acrylic resin film having excellent surface hardness and heat resistance that can be used for insert molding or in-mold molding (hereinafter referred to as an acrylic resin film molded product), a rubber-containing polymer having a specific composition, An acrylic resin film molded article obtained by mixing a thermoplastic polymer having a specific composition at a specific ratio has been proposed (see, for example, Patent Documents 1 and 2). Such an acrylic resin film molded product not only imparts decorativeness to the molded product, but also has a function as an alternative material for clear coating.
Further, the present applicant has proposed an acrylic resin film-like material that has excellent molding whitening properties during insert molding or in-mold molding, and has excellent surface hardness, heat resistance, and transparency (see, for example, Patent Document 3). .

In recent years, laminated products having an acrylic resin film layer on a surface layer formed by an insert molding method or an in-mold molding method have been used as parts for vehicle applications.
By containing a specific amount of a rubber-containing polymer having a specific average particle diameter, an acrylic resin film molded article excellent in surface hardness and heat resistance can be obtained (for example, see Patent Document 1). Moreover, the acrylic resin film molded article excellent in surface hardness and heat resistance is obtained by containing the rubber-containing polymer which consists of a specific multilayer structure in a specific amount (for example, refer patent document 2). Furthermore, by containing a specific amount of a rubber-containing polymer having a specific multilayer structure, an acrylic resin film molded product excellent in molding whitening property, surface hardness, and heat resistance can be obtained (for example, see Patent Document 3).
However, although these acrylic resin film molded articles have excellent properties as a skin material for vehicle interiors, they have a problem of low resistance to liquid agents, for example, sunscreen lotions.

JP-A-8-323934 Japanese Patent Laid-Open No. 11-147237 JP 2005-163003 A

  The present invention has a chemical resistance, for example, a film that does not roughen the surface of an acrylic resin film even when exposed to a high temperature for a long time with a lotion used to prevent sunburn, and is formed into a deep-drawn molded product. An object of the present invention is to provide an acrylic resin film for thermoforming that does not cause cracks on the surface, and has scratch resistance, surface hardness, and heat resistance, and a laminate molded product thereof.

The above object of the present invention is achieved by the following present invention.
[1] An acrylic resin film for thermoforming having an acrylic resin film and a 60 ° surface glossiness of 100% or more having a cured resin layer having a thickness of 2 to 12 μm as an outermost layer on one surface of the acrylic resin film.
[2] The thermoforming acrylic resin film of [1], wherein the cured resin layer is a resin obtained by curing an acrylic polyol resin and a polyisocyanate.
[3] The acrylic resin film for thermoforming according to [1] or [2], wherein the acrylic resin film has a pattern layer on a surface opposite to the cured resin layer of the acrylic resin film.
[4] A method for producing a thermoforming acrylic resin film according to the above [1] to [3], wherein the cured resin layer is formed by a printing method or a coating method.
[5] A laminate formed by laminating the acrylic resin film for thermoforming described in [1] to [3] on a base material so that a surface on the side opposite to the cured resin layer is in contact.
[6] The thermoforming acrylic resin film described in [1] to [3] is laminated on a base material by an in-mold molding method or an insert molding method so that a surface opposite to the cured resin layer is in contact. Laminated body.

  By adopting an acrylic resin film for thermoforming having a cured resin layer of 2-12 μm in thickness and having a 60 ° surface glossiness of 100% or more on one surface of the acrylic resin film of the present invention, a conventional acrylic Compared to resin film molded products, excellent chemical resistance is exhibited, and when insert molding or in-mold molding is performed to form a deep-drawn molded product, there is no cracking on the film surface, and the vehicle An acrylic resin film for thermoforming having scratch resistance, surface hardness, and heat resistance that can be used for applications and a laminate obtained by laminating the acrylic resin film can be provided.

<Acrylic resin film>
As the acrylic resin film used in the present invention, a publicly known acrylic resin film can be used, and it has characteristics such as scratch resistance, pencil hardness, heat resistance, and chemical resistance for vehicles. Those disclosed in Kaihei 8-323934, JP-A-11-147237, JP-A 2002-80678, JP-A 2002-80679, JP-A-2005-97351, and the like are preferable. Further, from the viewpoint of resistance to molding whitening when insert molding or in-mold molding is performed, those disclosed in JP-A-2005-163003 and JP-A-2005-139416 are preferable.

(Heat shrinkage)
As an acrylic resin film, the thing which does not shrink | contract as much as possible at the time of a heating is preferable. When the acrylic resin film for thermoforming is bonded to a base material sheet such as ABS and insert molding is performed, the acrylic resin film may be peeled off from the base material sheet when the acrylic resin film is greatly contracted.
Therefore, as the acrylic resin film in the present invention, an acrylic resin film having a heat shrinkage in the MD direction of 50% or less and a heat shrinkage in the TD direction of −10 to 10% by heat treatment at 130 ° C. for 60 minutes. preferable. In the case of using a laminated sheet obtained by laminating an acrylic resin film on a base material sheet as a decorative film or sheet, such an acrylic resin film is made of a base material sheet and an acrylic resin during heating during insert molding or in-mold molding. Prevents peeling at the interface with the resin film. It is preferable that the shrinkage rate during heating of the acrylic resin film is small. The MD direction heat shrinkage of the acrylic resin film is preferably 30% or less, and more preferably 15% or less. Moreover, 0% or more is preferable. The TD-direction heat shrinkage rate of the acrylic resin film is preferably 0 to 5%.

The measurement of the heat shrinkage rate was carried out on the surface of an acrylic resin film cut out to A4 size, in parallel in the MD direction (flow direction during film formation) and TD direction (direction perpendicular to the MD direction) at intervals of 5 cm. Draw a straight line and measure the distance accurately with calipers. The interval is measured at two locations, and the measured locations are marked. Thereafter, the sample is left in an atmosphere at 130 ° C. for 60 minutes and taken out, and then the interval between the same positions as previously measured is measured again. The heat shrinkage rate is calculated by the following formula using the average value of the distance between the two locations.
Heat shrinkage rate (%) = ((interval before heating−interval after heating) / interval before heating) × 100
In the acrylic resin film in which the MD direction and the TD direction are unknown, the MD direction and the TD direction are specified as follows, for example. Draw a circle with a specific radius on the film, heat-treat the conditions described above, and determine the direction in which the shrinkage rate is maximized from the shape of the circle (or ellipse if there is anisotropy) on the film. The direction is the MD direction, and the direction perpendicular to the MD direction is the TD direction.

(Pencil hardness)
The pencil hardness (measured based on JIS K5600) of the acrylic resin film is preferably 2B or more, more preferably HB or more, in order to increase the pencil hardness of the acrylic resin film for thermoforming of the present invention, F The above is particularly preferable.

(Method for producing acrylic resin film)
Examples of the method for producing the acrylic resin film include known methods such as a melt casting method such as a melt casting method, a T-die method, and an inflation method, and a calendar method. Of these, the T-die method is preferable from the viewpoint of economy.
When the acrylic resin film is formed by the T-die method, it is preferable to use a method of forming a film by sandwiching it between a plurality of rolls or belts selected from a metal roll, a non-metal roll and a metal belt. According to this method, the surface smoothness of the resulting acrylic resin film for thermoforming is improved, the coating is missing when the cured resin layer is formed on the acrylic resin film, and the printing is performed when the acrylic resin film for thermoforming is printed. Omission can be suppressed. As the metal roll, it is used in a sleeve touch method comprising a metal mirror surface touch roll; a metal sleeve (metal thin film pipe) described in Japanese Patent No. 2808251 or International Publication No. 97/28950, and a molding roll. Rolls and the like. Examples of the non-metallic roll include a touch roll made of silicon rubber. Examples of the metal belt include a metal endless belt. A plurality of these metal rolls, non-metal rolls and metal belts may be used in combination.

  In the method of forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts, the raw material after melt extrusion is sandwiched in a state where there is substantially no bank (resin pool). However, it is preferable to form a film by transferring the surface without substantially rolling. When the film is formed without forming a bank (resin pool), the raw material in the cooling process is surface-transferred without being rolled, so the heat shrinkage rate of the acrylic resin film substrate formed by this method is reduced. be able to. Moreover, when performing melt extrusion by the T-die method or the like, it is also preferable to extrude while filtering the acrylic resin raw material in a molten state with a screen mesh of 200 mesh or more.

  As for the thickness of an acrylic resin film, 10-500 micrometers is preferable. By setting the thickness of the acrylic resin film to 500 μm or less, rigidity suitable for insert molding and in-mold molding can be obtained, and the film can be manufactured more stably. Moreover, by making the thickness of the acrylic resin film 10 μm or more, a sense of depth can be more sufficiently imparted to the resulting laminate together with the protective properties of the film. The thickness of the acrylic resin film is more preferably 30 μm or more, and particularly preferably 50 μm or more. The upper limit is more preferably 300 μm or less, and particularly preferably 200 μm or less.

<Curing resin layer>
The cured resin layer is obtained by curing a curable resin.
The thickness of such a cured resin layer provided on one surface of the acrylic resin film needs to be 2 to 12 μm. When the thickness of the cured resin layer is 2 μm or more, chemical resistance when a laminated body is obtained can be exhibited. More preferably, it is 4 μm or more. If the thickness of the cured resin layer is 12 μm or less, the occurrence of cracks in the cured resin layer can be reduced even when insert molding or in-mold molding is performed to form a deep drawing shape. The thickness of the cured resin layer is preferably 8 μm or less. Moreover, since the coating amount per unit area used in the coating is reduced, it is possible to reduce the physical property deterioration of the acrylic resin film due to the solvent. In addition, the thickness of the cured resin layer is obtained by observing the cross section of the film with a transmission electron microscope, measuring the thickness at five locations, and averaging them.

(Curable resin)
As the curable resin, it is preferable to use a known thermosetting resin or photocurable resin from the viewpoints of chemical resistance, scratch resistance, and heat resistance. For example, acrylic resins, urethane acrylate resins, silicone acrylate resins, epoxy resins, and ester resins can be used. Of these, urethane acrylate resins are preferred from the viewpoint of physical properties. As the urethane acrylate resin, known resins can be used. In particular, the main component is a methacrylic acid alkyl ester unit, the hydroxyl value is 20 to 120 mgKOH / g, and the glass transition temperature is 50 to 110 ° C. A urethane acrylate thermosetting resin containing a hydroxyl group-containing acrylic resin and a polyisocyanate is preferred.
The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, from the viewpoint of chemical resistance and scratch resistance. The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, from the viewpoint of chemical resistance, adhesion, and cracking of the cured resin layer during molding.
The glass transition temperature of the hydroxyl group-containing acrylic resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of chemical resistance, heat resistance, film blocking properties, pencil hardness, scratch resistance, and the like.

  The polyisocyanate (curing agent) is not particularly limited, but isocyanurate composed of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and the like that cause little yellowing during heating. Type polyisocyanate, adduct type polyisocyanate with trimethylolpropane, and burette type polyisocyanate are preferable. In addition, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate can be used as they are.

The polyisocyanate is preferably used so as to have an addition amount corresponding to a range of 0.5 to 1.5 times the molar amount of the isocyanate group with respect to the molar amount of the hydroxyl group in the hydroxyl group-containing acrylic resin. By setting it to 0.5 times or more, the amount of isocyanate groups is sufficient with respect to the hydroxyl group, so that the curing is sufficiently advanced and chemical resistance and scratch resistance are improved. When the addition amount is 1.5 times or less, sufficient scratch resistance is exhibited, and the cured resin layer is hardly cracked during molding.
In addition, when a thermoplastic resin is used as the binder resin, although the moldability is good, the chemical resistance tends to decrease. When used for vehicle interiors, if a liquid agent such as sunscreen or fragrance adheres, the coat layer may melt and an appearance defect may occur.

<Acrylic resin film for thermoforming>
In the acrylic resin film for thermoforming of the present invention, the cured resin layer is formed on the acrylic resin film with a thickness of 2 to 12 μm, and the 60 ° surface glossiness is 100% or more.

(Method for forming cured resin layer)
It is preferable to form a cured resin layer by a printing method or a coating method. In this case, the cured resin layer is prepared by dissolving or dispersing the raw material to be the cured resin layer in a solvent to prepare a paint, applying it to one surface of the acrylic resin film, and performing heat drying for removing the solvent. Is formed. This method is preferable because the adhesion between the cured resin layer and the acrylic resin film becomes good.
Examples of the printing method include known printing methods such as gravure printing, screen printing, and offset printing.
Coating methods include flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, kiss reverse coating, micro gravure coating, roll coating, blade coating, rod coating, and roll doctor. Known coating methods such as a coating method, an air knife coating method, a comma roll coating method, a reverse roll coating method, a transfer roll coating method, a kiss roll coating method, a curtain coating method, and a dipping coating method may be mentioned.

In the case where a paint is applied on the acrylic resin film, the solvent contained in the paint applied per 1 m ^{2 of} the acrylic resin film is preferably 30 g or less, and 20 g or less, from the viewpoint of reducing physical properties of the acrylic resin film due to the solvent. Is more preferable, and 10 g or less is particularly preferable. In addition, the amount of the coating material to be applied needs to be an amount such that the thickness of the cured resin layer after drying is 2 to 12 μm. When the coating amount is such an amount that the thickness of the cured resin layer is 2 μm or more, the surface physical properties when a laminate is obtained can be expressed. Preferably it is 4 micrometers or more. If the amount of paint is such that the thickness of the cured resin layer is 12 μm or less, the amount of paint per unit area used in coating is reduced, so that the physical property deterioration of the acrylic resin film due to the solvent can be reduced. it can. The thickness of the cured resin layer is preferably 8 μm or less.

  As the solvent, a solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C., higher than the glass transition temperature of the burner resin (for example, acrylic polyol resin) is preferable because the solvent hardly remains in the thermoforming acrylic resin film. . In particular, each component of the curable resin can be dissolved or uniformly dispersed, and the physical properties (mechanical strength, transparency, etc.) of the acrylic resin film are not adversely affected in practice. A volatile solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C., higher than the glass transition temperature of the constituent resin component is preferable.

  Specific examples of the solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and ethylene glycol; aromatic solvents such as xylene, toluene and benzene; aliphatic hydrocarbon solvents such as hexane and pentane; Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; phenol solvents such as phenol and cresol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone; diethyl ether, methoxytoluene and 1,2-dimethoxyethane Ether solvents such as 1,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane and tetrahydrofuran (THF); fatty acid solvents such as formic acid, acetic acid and propionic acid An acid such as acetic anhydride Water-based solvents; ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate and butyl formate; nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide; sulfur-containing solvents such as thiophene and dimethyl sulfoxide; Diacetone alcohol, 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine, 1-acetoxy-2- Examples of the solvent include two or more kinds of functional groups such as ethoxyethane and 2-acetoxy-1-methoxypropane; various known solvents such as water. These can be used alone or in combination of two or more.

  Among these, a solvent mainly composed of ethyl acetate, n-propyl acetate, isopropyl alcohol, methyl ethyl ketone, and methyl isobutyl ketone is preferable because the influence of the physical properties of the acrylic resin fill due to the solvent is reduced. Moreover, it is preferable to use butyl acetate and methyl isobutyl ketone together from the viewpoint of the adhesiveness between the cured resin layer and the acrylic resin film. From the viewpoint of gloss after coating, it is preferable to use a medium boiling solvent such as butyl acetate and methyl isobutyl ketone and a high boiling solvent such as 2-acetoxy-1-methoxypropane and cyclohexanone in combination. Moreover, it is preferable to filter the coating material for the purpose of removing foreign substances from the viewpoint of reducing omission of coating and reducing the generation of doctor streaks. Filtration may be performed after preparation of the paint, or may be performed immediately before coating or while coating. Although this filtration can be carried out with a known filtration device, CPII-10, 03, 01 manufactured by Chisso Filter Co., Ltd. is suitable.

For paints, known additives for improving solution properties such as anti-skinning agents, thickeners, anti-settling agents, anti-sagging agents, antifoaming agents, leveling agents, etc .; light stabilizers, UV absorbers, oxidation Known additives for improving the coating film performance such as an inhibitor, an antibacterial agent, an antifungal agent and a flame retardant can be added. After coating, it is preferable to stand for several hours to several days in an atmosphere of 30 to 80 ° C. in order to make the cured resin layer have a sufficient crosslinking density. The standing time is set according to the type of polyisocyanate, the heat resistance of the acrylic resin film, etc. As an example, when polyhexamethylene diisocyanate is used, it has a sufficient crosslinking density under the conditions of 40 ° C. and 48 hours. A resin layer is obtained.
Usually, in order to form a coating film having a sufficient thickness on a molded product by coating, it may be necessary to apply several tens of times, and in this case, the cost is high and the productivity is not so good. On the other hand, the laminate of the present invention has a high industrial utility value because the thermoforming acrylic resin film itself becomes a coating film, so that the number of repeated coatings is small.

(Pencil hardness of acrylic resin film for thermoforming)
The acrylic resin film for thermoforming of the present invention preferably has a pencil hardness (measurement based on JIS K5600) of 2B or more. By setting the pencil hardness to 2B or more, the surface of the acrylic resin film for thermoforming is hardly scratched during the process of insert molding or in-mold molding, and the scratch resistance of the laminate is improved. Considering the case where it is used for a laminate such as a vehicle member, the pencil hardness of the thermoforming acrylic resin film of the present invention is preferably HB or more. A laminate using a thermoforming acrylic resin film having a pencil hardness of HB or higher can be suitably used for various vehicle members such as a door waist garnish, a front control panel, a power window switch panel, and an airbag cover. It is very useful industrially from the viewpoint of expanding applications.

  Furthermore, when the pencil hardness of the acrylic resin film for thermoforming of the present invention is F or more, the scratches are not noticeable even when scratched with a cloth having a rough surface such as gauze, and the acrylic resin film for thermoforming having a pencil hardness of 2H is used. The industrial use value is very high because practical scratch resistance equivalent to that of the laminated body can be imparted. In order to obtain an acrylic resin film for thermoforming having such pencil hardness, the pencil hardness of the acrylic resin film serving as a base material is important. The acrylic hardness of the acrylic resin film serving as the base material is preferably 2B or higher, more preferably HB or higher, and most preferably F or higher.

(Haze value)
The haze value of the thermoforming acrylic resin film is preferably 2% or less, and more preferably 1% or less, from the viewpoint of designability when the picture layer is viewed through the thermoforming acrylic resin film. The haze value is a value measured by a test method of JIS K7136.
<Pattern layer>
A pattern layer may be formed on the acrylic resin film for thermoforming of the present invention in order to impart design properties to various substrates. In this case, it is preferable to form a picture layer on the surface of the acrylic resin film opposite to the surface on which the cured resin layer is provided. Moreover, at the time of manufacture of a laminated body, it is preferable from the point of protection of a decorating surface and provision of a high-class feeling to distribute a pattern layer to the adhesive surface with a base material. The pattern layer is preferably formed by a printing method or a vapor deposition method.

(Print layer)
The printed layer becomes a pattern or characters on the surface of the laminate obtained by insert or in-mold molding. Examples of the print pattern include a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, full face, and the like.
As binders for the printing layer, polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose Examples of the resin include ester resins, alkyd resins, and chlorinated polyolefin resins.
For the formation of the printing layer, a colored ink containing a binder and an appropriate color pigment or dye as a colorant may be used.
Examples of the pigment include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as chrome lead. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals. Examples of the blue pigment include organic pigments such as phthalocyanine blue; inorganic pigments such as cobalt blue. Examples of the black pigment include organic pigments such as aniline black. Examples of the white pigment include inorganic pigments such as titanium dioxide.
Moreover, as a dye, various well-known dyes can be used in the range which does not impair the effect of this invention.

Examples of the method for forming the printing 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 printing layer may be appropriately determined as necessary, and is usually about 0.5 to 30 μm.
The number of missing prints in the print layer is preferably 10 pieces / m ² or less from the viewpoints of design properties and decorating properties. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminate using the thermoforming acrylic resin film becomes better. The number of missing prints in the print layer is more preferably 5 pieces / m ² or less, and particularly preferably 1 piece / m ² or less.
The thickness of the printed layer may be appropriately selected according to the degree of extension during the insert or in-mold molding so that a desired surface appearance can be obtained in the laminate obtained by the insert or in-mold molding.

(Deposition layer)
The vapor deposition layer is formed of at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or an alloy or compound thereof. The Examples of the method for forming the vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and plating.
The thickness of a vapor deposition layer is suitably selected according to the expansion | extension degree at the time of insert or in-mold shaping | molding so that a desired surface appearance may be obtained in the laminated body obtained by insert or in-mold shaping | molding.

<Other layers>
(Adhesive layer)
The acrylic resin film for thermoforming of the present invention may be provided with an adhesive layer as necessary. The adhesive layer is preferably formed on the surface opposite to the surface on which the cured resin layer is provided.
(Cover film)
Moreover, you may provide a cover film further in the acrylic resin film for thermoforming of this invention. This cover film is effective for dust-proofing the surface of the thermoforming acrylic resin film. The cover film can be provided on either the surface of the cured resin layer or the surface opposite to the surface on which the cured resin layer is provided, but is preferably provided on the surface of the cured resin layer. When the cover film is provided on the surface of the cured resin layer, the cover film adheres to the cured resin layer before in-mold and insert molding, and immediately peels off when in-mold and insert molding. Therefore, it is necessary to have appropriate adhesion and good releasability. As the cover film, any film can be selected and used as long as it satisfies such conditions. Examples of such a film include a polyethylene film, a polypropylene film, and a polyester film.

(Thermoplastic resin layer)
The acrylic resin film for thermoforming of the present invention may be further laminated on a thermoplastic resin layer to form a laminated film or sheet. The direction in which the acrylic resin film for thermoforming is laminated on the thermoplastic resin layer is preferably laminated so that the surface opposite to the surface on which the cured resin layer is provided is in contact with the thermoplastic resin layer. The thermoplastic resin layer is preferably made of a material having compatibility with the base material for the purpose of improving the adhesion with the base material. More preferably, the thermoplastic resin layer is made of the same material as the base material. As the thermoplastic resin layer, a known thermoplastic resin film or sheet can be used. For example, acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer); Vinyl resin;

  Polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene; Polyolefin copolymers such as ethylene-vinyl acetate copolymer or saponified product thereof, ethylene- (meth) acrylate copolymer; polyethylene terephthalate, poly Polyester resins such as butylene terephthalate, polyethylene naphthalate, polyarylate, and polycarbonate; polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, and 12-nylon; polystyrene resins; cellulose acetate, nitrocellulose Fibrin derivatives such as: Fluorine resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, etc .; or two or three selected from these Copolymers or mixtures of the above, complex, laminates, and the like.

Among these, as the thermoplastic resin layer, acrylic resin, ABS resin, vinyl chloride resin, polyolefin, and polycarbonate are preferable from the viewpoint of formability of the pattern layer and secondary moldability of the laminated film or sheet.
If necessary, the thermoplastic resin layer may contain general compounding agents such as stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents, and antifungal agents. An agent, a release agent, an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant, and the like may be blended.
The thickness of the thermoplastic resin layer may be appropriately determined as necessary, and is usually preferably about 20 to 500 μm. The thermoplastic resin layer preferably has a thickness such that the appearance of the thermoplastic acrylic resin film has a completely smooth upper surface, absorbs surface defects of the base material, or does not disappear the pattern layer during injection molding.

Examples of a method for obtaining a laminated film or sheet include known methods such as thermal lamination, dry lamination, wet lamination, and hot melt lamination. Moreover, the acrylic resin film for thermoforming and the thermoplastic resin layer can be laminated by extrusion lamination.
By using the thermoforming acrylic resin film of the present invention as a laminated film or sheet, a sufficient strength for handling against external forces such as impact and deformation is exhibited. For example, cracks and the like are less likely to occur when the film is vacuum-molded by insert molding or the like and then removed from the mold, or when the vacuum-molded product is mounted on an injection mold. , Handling becomes good. Furthermore, for example, the surface defect of the injection-molded base material is minimized to be propagated to the thermoforming acrylic resin film, or the pattern layer is less likely to disappear when the base material is injection-molded. give.
For example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, anchor, primer on one surface of the acrylic resin film for thermoforming, the surface of the thermoplastic resin layer of the laminated film or sheet Surface treatment such as treatment may be performed. These treatments include adhesion between the thermoforming acrylic resin film and the cured resin layer or the picture layer, between the thermoplastic resin layer and the picture layer, between the thermoforming acrylic resin film and the thermoplastic resin layer, etc. Improve sexiness.

<Laminated body>
The laminate of the present invention is obtained by laminating a thermoforming acrylic resin film, a laminated film or a sheet thereof on a base material. At this time, it is preferable to laminate so that the surface opposite to the surface on which the cured resin layer is provided is in contact with the substrate. Examples of the material of the base material include: resin; wood board such as wood veneer, wood plywood, particle board, medium density fiber board (MDF); water quality board such as wood fiber board; metal such as iron and aluminum.
The type of resin is not particularly limited. For example, polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefinic thermoplastic elastomer;

  General-purpose thermoplastic or thermosetting such as polystyrene resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin General-purpose engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetals, polycarbonate-modified polyphenylene ethers, polyethylene terephthalates; Super engineering resin, etc .; reinforcement of glass fiber or inorganic filler (talc, calcium carbonate, silica, mica, etc.) , Composite resin, or various modified resins were added modifiers, such as the rubber component.

  Among these, as the material for the base material, a thermoforming acrylic resin film, a laminated film or a sheet that can be melt-bonded is preferable. For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or a resin containing these as main components can be given. In terms of adhesiveness, an ABS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin, or a resin containing these as a main component is preferable, and an ABS resin, a polycarbonate resin, or a resin containing these as a main component is more preferable. Even if it is a resin that is not heat-sealed, such as a polyolefin-based resin, by providing an adhesive layer, one selected from the group consisting of an acrylic resin film for thermoforming, a laminated film, or a sheet thereof is bonded to the base material at the time of molding. It is possible.

As a method for producing the laminate of the present invention, a known method such as thermal lamination can be used in the case of a two-dimensional laminate and when the substrate can be heat-sealed. For example, for wood substrates such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), water quality boards such as wood fiber board, metals such as iron and aluminum, etc. It is possible to bond them through an adhesive layer.
In the case of a three-dimensional laminate, a known method such as an insert molding method or an in-mold molding method can be used.
The in-mold molding method is a method of heating an acrylic resin film for thermoforming, or a laminated film or sheet thereof, and then vacuum-forming in a mold having a vacuuming function, and then a resin to be a base material in the same mold Is a method of obtaining a laminate in which an acrylic resin film for thermoforming, or a laminated film or sheet thereof and a substrate are integrated. The in-mold molding method is preferable from the viewpoints of workability and economy because the film molding and injection molding can be performed in one step.
A laminated film or sheet having a thermoplastic resin layer is preferred in that the disappearance of the pattern layer can be further reduced because of the presence of the thermoplastic resin layer.

  The heating temperature during the in-mold molding is preferably equal to or higher than the temperature at which the thermoforming acrylic resin film or sheet is softened. Specifically, it may be appropriately set depending on the thermal properties of the film or the shape of the laminate, and is usually 70 ° C. or higher. On the other hand, if the temperature is too high, the surface appearance tends to deteriorate or the releasability tends to deteriorate. This may be set as appropriate depending on the thermal properties of the film or the shape of the laminate, and is usually 170 ° C. or lower. Furthermore, from the viewpoint of energy efficiency, it is preferable that the preheating temperature during vacuum forming is low. Specifically, 135 ° C. or lower is preferable. In addition, a film that can be molded even when the preheating temperature is low can shorten the preheating time instead of lowering the preheating temperature. In this case, high-cycle vacuum forming is possible, and industrial utility value is high.

When a three-dimensional shape is imparted to a film by vacuum forming, the acrylic resin film for thermoforming of the present invention, its laminated film or sheet has a high degree of elongation at high temperatures, which is very advantageous.
As the resin to be injection-molded, any resin that can be injection-molded can be used regardless of the type. It is possible to approximate the shrinkage rate of the resin after injection molding to the shrinkage rate of the acrylic resin film for thermoforming, its laminated film or sheet, warping of the laminate obtained by in-mold molding or insert molding, This is preferable because problems such as peeling are eliminated.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. In the examples, “part” represents “part by mass”, and “%” represents “% by mass”. Abbreviated symbols in the examples are as shown in Table 1.

[Measurement and evaluation method of physical properties]
Physical properties of rubber-containing multistage polymer (I) and rubber-containing polymer (II), thermoplastic polymer (III), thermoplastic polymer (IV) and thermoplastic polymer (V), prepared acrylic resin film substrate ( A), the physical properties of the acrylic resin film substrate (B), Examples 1 to 5, and the acrylic resin film for thermoforming obtained in Comparative Examples 1 to 3 and laminates were measured and evaluated by the following methods. In addition, evaluation of the laminated body was performed using the laminated body produced for the evaluation of the moldability shown in the following ().

(1) Mass average particle diameter of rubber-containing multistage polymer (I) and rubber-containing polymer (II):
About the polymer latex of rubber-containing multistage polymer (I) and rubber-containing polymer (II) obtained by emulsion polymerization, a light scattering photometer DLS-700 (trade name: manufactured by Otsuka Electronics Co., Ltd.) was used. And measured by a dynamic light scattering method.
(2) Gel content of rubber-containing multistage polymer (I) and rubber-containing polymer (II):
A predetermined amount (mass before extraction) of the rubber-containing multistage polymer (I) and the rubber-containing polymer (II) (the coagulated powder obtained after polymerization) are extracted in an acetone solvent under reflux, It fractionated by centrifugation, the mass of acetone insoluble matter was measured after drying (mass after extraction), and it computed with the following formula.
Gel content (%) = mass after extraction (g) / mass before extraction (g) × 100

(3) Glass transition temperature (Tg) of rubber-containing multistage polymer (I), rubber-containing polymer (II), and binder resin:
It calculated from the formula of FOX using the value described in the polymer handbook (J. Brandrup, Interscience, 1989).
(4) Reduced viscosity of thermoplastic polymer (III), thermoplastic polymer (IV), thermoplastic polymer (V):
0.1 g of the polymer was dissolved in 100 mL of chloroform and measured at 25 ° C.

(5) Hydroxyl value of binder resin:
It measured according to JIS K0070.
(6) Mass average molecular weight of binder resin:
Using Shimadzu LC-6A system (manufactured by Shimadzu Corp.) and connecting three KF-805L (manufactured by Showa Denko KK) as a GPC column, using THF as a solvent, measured in terms of polystyrene did.
(7) Thickness of the cured resin layer of the acrylic resin film for thermoforming:
A sample obtained by cutting the acrylic resin film for thermoforming to a thickness of 70 nm in the cross-sectional direction is observed with a transmission electron microscope (J100S manufactured by JEOL Ltd.), the thickness is measured at five locations, and they are averaged. Thus, the thickness of the cured resin layer was obtained.

(8) Pencil hardness of acrylic resin film for thermoforming:
It measured according to JIS K5400. In addition, the pencil hardness of the surface of the cured resin layer was measured.
(9) Surface gloss of thermoforming acrylic resin film:
According to JIS Z8741, surface gloss at 60 ° was measured using a gloss meter (manufactured by Minolta, Multi-Gloss 268 type (trade name)). The film was measured on a black paper having a 60 ° gloss of 1% or less.

(10) Haze of acrylic resin film for thermoforming:
Evaluation was made according to JIS K7136.
(11) In-mold moldability of acrylic resin film for thermoforming:
In-mold molding was performed using an acrylic resin film for thermoforming.
Specifically, using a mold having a vacuum drawing function and having a recess of 1 cm ² and a depth of 1 mm at a position 3 cm laterally from the bottom of the mold on the cavity side and the center gate, In-mold molding was performed with an in-mold molding apparatus that combines a J85 ELII type injection molding machine (trade name, manufactured by Nippon Steel Works, Ltd.) and a hot pack system (trade name, manufactured by Nissha Printing Co., Ltd.).
The shape of the laminated body is a box shape having a length of 150 mm × width of 120 mm × thickness of 2 mm and a depth of 10 mm. The gate shape is a pinpoint gate having a diameter of 1 mm. The corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. That is, the corner R of the laminate on which the acrylic resin film is laminated is about 3. The corner R was measured with RADIUS GAGE manufactured by FUJI TOOL.

Vacuum forming of the acrylic resin film for thermoforming was performed under the conditions of a heater set temperature of about 330 ° C., a heating time of 15 seconds, and a distance between the heater and the film of 15 mm, and vacuum forming was performed so that the cured resin layer was in contact with the mold. .
Further, in the injection molding performed continuously in the same mold, the base resin was injected from the non-curable resin layer under the conditions of a cylinder temperature of 250 ° C., an injection speed of 30%, an injection pressure of 43%, and a mold temperature of 60 ° C. . As the base resin, heat-resistant ABS resin (trade name “Bulksum TM25B” manufactured by UMG ABS Co., Ltd.) was used.
The state of 1 cm ² formed on the obtained laminate, a convex portion having a height of 1 mm, or the vicinity of the corner of the laminate edge was observed and evaluated as follows.

(About cracking of convex part)
○: No cracking ×: Cracking occurred in the cured resin layer (for cracks near corners)
○: No cracking ×: Cracking occurred in the cured resin layer (Regarding whitening of the protrusions)
○: No whitening of film ×: Strong whitening of film (Regarding whitening near corners)
○: No film whitening ×: Strong film whitening

(12) Scratch resistance of the laminate:
The laminated body was pressed while applying a load of 0.01 MPa on the No. 60 broad sheet, and the laminated body was reciprocated 1000 at a stroke width of 100 mm and at a speed of 30 reciprocations / minute. The amount of change in the 60 ° gloss value of the rubbing test part before and after the test was evaluated as follows.
The 60 ° glossiness is an average value of four locations.
◎: The value obtained by subtracting the gloss after the test from the gloss before the test is less than 3 ○: The value obtained by subtracting the gloss after the test from the gloss before the test is 3 or more and less than 10 ×: From the gloss before the test The value obtained by subtracting the glossiness after the test is 10 or more.

(13) Chemical resistance of the laminated body Drop a drop of Copatone (Water BABIES 30SFP) on the surface of the laminated molded article, cover it with a 1cm square cotton cloth, place a 4cm square, 3mm thick aluminum plate on it, and A 500 g weight was placed on the aluminum plate and allowed to stand at a predetermined temperature for 24 hours. After the test, the test piece is washed with water and then air-dried, and the surface state of the test part is observed.
○: No change Δ1: The shape of the cotton cloth is transferred Δ2: The shape of the cotton cloth is not transferred but is slightly white ×: The shape of the cotton cloth is strongly transferred and becomes white

[Production Example 1] (Production of rubber-containing multistage polymer (I))
After charging 10.8 parts of deionized water into a vessel equipped with a stirrer, MMA 0.3 part, n-BA 4.5 part, 1,3-BD 0.2 part, AMA 0.05 part and CHP 0 A monomer component consisting of 0.025 parts was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “Phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.
Next, 139.2 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 75 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was added dropwise to the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the first stage polymerization of the elastic polymer (IA-1). ). Subsequently, a monomer component consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1.0 part of 1,3-BD, and 0.25 part of AMA, together with 0.016 part of CHP, is added over 90 minutes. After dropping into the polymerization vessel, the reaction was continued for 60 minutes to complete the polymerization of the second stage polymer of the elastic polymer (IA-2), and the elastic polymer (IA) was obtained.
Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of MA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes. A coalescence (IB) was formed.

Subsequently, after dropping a monomer component consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of n-OM and 0.075 part of t-BH over 140 minutes, the reaction is continued for 60 minutes, A hard polymer (IC) was formed to obtain a polymer latex of a rubber-containing multistage polymer (I). The Tg of the hard polymer (IC) alone was 99 ° C. Moreover, the mass average particle diameter of the rubber-containing multistage polymer (I) measured after polymerization was 0.11 μm.
The polymer latex of the rubber-containing multistage polymer (I) thus obtained was filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then 3.5 parts of calcium acetate. It was salted out in an aqueous solution containing, washed with water, collected, and dried to obtain a powdery rubber-containing multistage polymer (I). The gel content of the rubber-containing multistage polymer (I) was 70%.
Further, 214.3 g of the obtained rubber-containing multistage polymer (I) was added to 1500 ml of acetone filtered through a nylon mesh having an opening of 25 μm, and stirred for 3 hours to obtain an acetone dispersion of the rubber-containing multistage polymer (I). Was prepared. Next, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was washed in chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Next, the captured substance after ultrasonic cleaning is put into 150 ml of acetone filtered through a nylon mesh having a mesh size of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes. 150 ml of an acetone dispersion of the trapped material was prepared. Next, 70 ml of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (Rion Co., Ltd., model: KL-01), and the number of particles having a diameter of 55 μm or more was determined. It was a piece.

[Production Example 2] (Production of rubber-containing polymer (II))
Under a nitrogen atmosphere, 244 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, and the temperature was raised to 80 ° C. And (i) shown in Table 2 was added, and while stirring, 1/15 of the raw material (b) for the first stage polymer (II-A-1) shown in Table 3 was charged, Hold for 15 minutes. Next, the remaining raw material (b) is continuously added at a rate such that the rate of increase of the monomer component [raw material (b)] with respect to water is 8% / hour, and then held for 60 minutes to obtain an elastic polymer. A latex of the first stage polymer (II-A-1) was obtained. Subsequently, 0.6 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (c) for the second stage polymer (II-A-2) of the elastic polymer shown in Table 2 was added to the monomer component [raw material ( C)] is continuously added at a rate of 4% / hour and then held for 120 minutes to form a second-stage polymer (II-A-2) of an elastic polymer. A latex of combined (II-A) was obtained. Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. And while stirring at 80 degreeC in nitrogen atmosphere, the increase rate of the monomer component [raw material (ni)] with respect to water is 10 for the raw material (d) for hard polymer (II-C) shown in Table 2. After the continuous addition at a rate of% / hour, the mixture was held for 60 minutes to form a hard polymer (II-C) to obtain a polymer latex of a rubber-containing polymer (II). The Tg of the hard polymer (II-C) alone was 99 ° C. Moreover, the mass average particle diameter of the rubber-containing polymer (II) measured after polymerization was 0.28 μm.
Calcium acetate is added to the polymer latex of the obtained rubber-containing polymer (II), and coagulation, aggregation and solidification are performed, followed by filtration, washing with water, and drying to obtain a powdery rubber-containing polymer (II ) The gel content was 90%.

[Production Example 3] (Production of thermoplastic polymer (III))
The reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and as an emulsifier, 1 part of “Latemul ASK” (trade name: manufactured by Kao Corporation) and 0.15 part of potassium persulfate were charged.
Next, 40 parts of MMA, 2 parts of n-BA and 0.004 part of n-OM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization.
Subsequently, a monomer component consisting of 44 parts of MMA and 14 parts of n-BA was added dropwise over 2 hours, and then held for 2 hours to complete the polymerization.
The obtained polymer latex of the thermoplastic polymer (III) is added to a 0.25% aqueous sulfuric acid solution, and the polymer is acidified, and then dehydrated, washed with water and dried to obtain a powdery thermoplastic polymer ( III) was recovered. The reduced viscosity of the obtained thermoplastic polymer (III) was 0.38 L / g.

[Production Example 4] (Production of thermoplastic polymer (IV))
(I) Production of Anionic Polymer Compound Aqueous Solution (A1) as Dispersion Stabilizer In a polymerization apparatus equipped with a stirrer, 58 parts of 2-sulfoethyl sodium methacrylate, potassium methacrylate aqueous solution (potassium methacrylate content 30%) 31 A monomer mixture consisting of 11 parts of methyl methacrylate and 900 parts of deionized water were added and dissolved by stirring. Thereafter, the mixture was heated to 60 ° C. with stirring under a nitrogen atmosphere, and kept at 60 ° C. with stirring for 6 hours to obtain an aqueous anionic polymer compound solution. At this time, after the temperature reached 50 ° C., 0.1 part of ammonium persulfate was added as a polymerization initiator, and 11 parts of methyl methacrylate weighed separately was added dropwise to the reaction system over 75 minutes. did.
Let the anionic polymer compound aqueous solution obtained by the above-mentioned manufacturing method be (A1).

(Ii) Production of Anionic Polymer Compound Aqueous Solution (A2) as Dispersion Stabilizer A polymerization apparatus equipped with a stirrer was charged with 68 parts of potassium hydroxide aqueous solution (potassium hydroxide content 17.1%) and 32 parts of methyl methacrylate. Stir the resulting mixture. After completion of the saponification reaction, the temperature of the mixture was raised to 80 ° C. and kept at 80 ° C. while stirring for 4 hours to obtain an aqueous anionic polymer compound solution. At this time, after the temperature reached 72 ° C., 0.1 part of ammonium persulfate was added as a polymerization initiator. Thereafter, 1000 parts of deionized water was dividedly charged into a polymerization apparatus equipped with a stirrer, and at the same time, an aqueous anionic polymer compound solution was transferred and collected in a container equipped with a stirrer. Let the anionic polymer compound aqueous solution obtained by the above-mentioned manufacturing method be (A2).

(Iii) Suspension polymerization method In a separable flask having an internal volume of 10 liters equipped with a stirrer, 6000 ml of deionized water was added, and 4 g of the aqueous anionic polymer compound (A1) obtained in (i) above as a dispersion stabilizer. 1 g of the anionic polymer compound aqueous solution (A2) obtained in (ii) above and 9 g of sodium sulfate as a dispersion stabilizing aid were added and stirred and dissolved. In addition, to a monomer mixture of MMA 2700 g and MA 300 g prepared in a separate container equipped with a stirrer, add 3 g of AIBN as a polymerization initiator, n-OM 6.6 g as a chain transfer agent, and S100A 6 g as a release agent, and stir and dissolve. It was. This monomer mixture was put into a separable flask having an internal volume of 10 L equipped with the stirrer equipment, and stirred for 15 minutes at a rotation speed of 300 stirrer while purging with nitrogen. Thereafter, the polymerization was started by heating to 80 ° C., and after completion of the polymerization exothermic peak, a heat treatment was performed at 95 ° C. for 60 minutes to complete the polymerization.
The polymer-containing aqueous solution obtained by this suspension polymerization method was dehydrated, washed with water and dried, and then the powdered thermoplastic polymer (IV) was recovered. This thermoplastic polymer (IV) was dissolved in 0.1 g of chloroform (100 ml), and the reduced viscosity was measured at 25 ° C. As a result, it was 0.06 liter / g.

[Production Example 5] (Production of thermoplastic polymer (V))
It carried out by the same suspension polymerization method except having changed into MMA2940g and MA60g among the manufacturing methods of the thermoplastic polymer (IV) of said [manufacture example 4]. This thermoplastic polymer (V) was dissolved in 0.1 g of chloroform (100 ml), and the reduced viscosity was measured at 25 ° C. As a result, it was 0.06 liter / g.

[Production Example 6] (Production of acrylic resin film (A))
75 parts of rubber-containing multistage polymer (I) and thermoplastic polymer (V) [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g) ] 25 parts, "Tinuvin 234" (trade name: manufactured by Ciba Specialty Chemicals) 1.4 parts, "Adekastab AO-50" 0.1 part and "Adekastab LA-67" (all are trade names: After adding 0.3 part of Asahi Denka Kogyo Co., Ltd., it was mixed using a Henschel mixer. This mixture was supplied to a degassing extruder heated to 230 ° C. (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.), kneaded, extruded while removing foreign matter with a 300 mesh screen mesh, and pellets Got.
The pellets produced by the above method were dried at 80 ° C. all day and night, and a cylinder temperature of 180 to 240 ° C. was used using a 40 mmφ non-vent screw extruder (L / D = 26) equipped with a 300 mm wide T-die. Then, extruding while removing foreign matter with a 500 mesh screen mesh, passing the molten acrylic resin film extruded under the conditions of T-die temperature of 240 ° C. and T-die slit width of 0.3 mm between two metal cooling rolls After sandwiching the resin without any bank (resin reservoir), transferring the surface without rolling, and winding it around a paper roll with a winder, an acrylic resin film (A) having a thickness of 125 μm was formed. . The acrylic hardness of the acrylic resin film (A) was H.

[Production Example 7] (Production of acrylic resin film (B))
16 parts of rubber-containing polymer (II) and thermoplastic polymer (IV) [MMA / MA copolymer (MMA / MA = 90/10 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] 84 parts, thermoplastic polymer (III) 1 part as a compounding agent, “Tinuvin 234” (trade name: manufactured by Ciba Specialty Chemicals) 1.4 parts, “Adeka Stub AO-50” 0.1 part and “Adeka Stub LA” After adding 0.3 part of “-67” (trade name: manufactured by Asahi Denka Kogyo Co., Ltd.), the mixture was mixed using a Henschel mixer. This mixture was supplied to a degassing extruder heated to 230 ° C. (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.), kneaded, extruded while removing foreign matter with a 300 mesh screen mesh, and pellets Got.
An acrylic resin film (B) having a thickness of 125 μm was formed in the same manner as the acrylic resin film (A) except that the pellets produced by the above method were used.
The acrylic resin film (B) had a pencil hardness of 2H.

[Example 1]
30 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, glass transition temperature 90 ° C., mass average molecular weight about 80,000), which is a copolymer of MMA 85%, HEMA 12%, n-BA 3%, hexamethylene diisocyanate 7.1 parts of (isocyanurate type) trimer was dispersed in a solvent consisting of 2.4 parts of ethyl acetate, 30 parts of butyl acetate, 25 parts of methyl ethyl ketone, and 35 parts of methyl isobutyl ketone to obtain a paint.
Next, after applying onto one side of a 125 μm thick acrylic resin film (A) using a baker-type applicator (memory set to 2), the solvent is volatilized at 80 ° C. for 10 minutes and thermoformed. An acrylic resin film was obtained. The acrylic resin film for thermoforming was aged at 40 ° C. for 2 days to cure the curable resin. The thickness of the cured resin layer was 5 μm.
Thereafter, the obtained acrylic resin film for thermoforming was in-mold molded to obtain a laminated molded product.

[Example 2]
It implemented like Example 1 except using a 125-micrometer-thick acrylic resin film (B).

Example 3
The same evaluation as in Example 1 was performed except that the memory of the Baker type applicator was set to 3 and applied. The thickness of the cured resin layer obtained after curing was 9 μm.

Example 4
29.3 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 104 mg KOH / g, glass transition temperature 86 ° C., mass average molecular weight about 80,000), which is a copolymer of MMA 77%, HEMA 20%, n-BA 3%, hexa The same operation as in Example 1 was carried out except that a proportion of 8.7 parts of a trimer of methylene diisocyanate (isocyanurate type) was blended.
The thickness of the cured resin layer obtained after curing was 5 μm.

Example 5
The same evaluation as in Example 4 was performed except that the memory of the baker type applicator was set to 1 and applied.
The cured resin layer obtained after curing had a thickness of 2 μm.
From the evaluation results in Table 3, it was confirmed that Examples 1 to 5 had good moldability and excellent chemical resistance.

[Comparative Example 1]
The same evaluation as in Example 1 was performed except that the memory of the Baker type applicator was set to 4 and applied.
The cured resin layer obtained after curing had a thickness of 15 μm.
From the evaluation results in Table 3, cracks at the corners of the laminate were confirmed in the moldability evaluation.

[Comparative Example 2]
The same evaluation as in Example 1 was performed except that the acrylic resin film (A) was used as it was and in-mold molded to obtain a laminated molded product.
From the evaluation results in Table 3, the surface layer of the laminated molded product subjected to the chemical resistance test was slightly white although the shape of the cotton cloth was not transferred.
Table 3 summarizes the evaluation results of the acrylic resin film substrate, the thermoforming acrylic resin film, and the laminate obtained as described above.

  As described above, by employing the thermoforming acrylic resin film having the configuration of the present invention, it exhibits excellent chemical resistance as compared with conventional acrylic resin films, and has good handling properties. Even when insert molding or in-mold molding is performed to form a deep-drawn molded product, the film surface does not crack and has heat resistance, surface hardness, and heat resistance that can be used for vehicle applications. An acrylic resin film for molding and a laminate in which these are laminated on a substrate can be provided.

  The laminated molded article having the acrylic resin film for thermoforming of the present invention is particularly suitable for vehicle use and building material use. Specific examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior applications, weather strips, bumpers, bumper guards, side mud guards, body panels, Spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, and other automotive exterior applications, AV equipment and furniture products Applications such as front panels, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons, etc. Building interior materials such as surfaces, ceilings, floors, exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates, and windbreak boards, window frames, doors, railings, sills, and surfaces of furniture Cosmetic materials, various displays, lenses, mirrors, goggles, window glass and other optical components, trains, airplanes, ships and other vehicles other than automobiles, interior and exterior applications, bottles, cosmetic containers, various packaging such as accessories It can be suitably used for various other uses such as containers and materials, miscellaneous goods such as prizes and accessories.

Claims (6)

  A thermoforming acrylic resin film having an acrylic resin film and a cured resin layer having a thickness of 2 to 12 μm as an outermost layer on one surface of the acrylic resin film and having a 60 ° surface glossiness of 100% or more.   2. The acrylic resin film for thermoforming according to claim 1, wherein the cured resin layer is a resin obtained by curing an acrylic polyol resin and a polyisocyanate.   The acrylic resin film for thermoforming according to claim 1 or 2, further comprising a pattern layer on a surface opposite to the cured resin layer.   The method for producing an acrylic resin film for thermoforming according to any one of claims 1 to 3, wherein the cured resin layer is formed by a printing method or a coating method.   The laminated body formed by laminating | stacking the acrylic resin film for thermoforming in any one of the said Claims 1-3 on a base material so that the surface on the opposite side to the cured resin layer may contact | connect.   Lamination obtained by laminating the thermoforming acrylic resin film according to any one of claims 1 to 3 on a substrate by an in-mold molding method or an insert molding method so that a surface opposite to the cured resin layer is in contact body.