JP2023080524A - (Meth)acrylic resin composition - Google Patents

Abstract

To maintain antiviral property, transparency, and anti-static property.SOLUTION: A (meth)acrylic resin composition includes a (meth)acrylic resin, a vinylidene fluoride resin, and a glycerine fatty acid ester, where the glycerine fatty acid ester is a glycerine fatty acid ester having a HLB value within the range of 5 or higher and 12 or lower, when the total content of the (meth)acrylic resin, the vinylidene fluoride resin, and the glycerine fatty acid ester is 100 mass%, the content of the (meth)acrylic resin is within the range of 40 mass% or more and 84 mass% or less, the content of the vinylidene fluoride resin is within the range of 15 mass% or more and 50 mass% or less, and the content of the glycerine fatty acid ester is 1 mass% or more and 10 mass% or less.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a (meth)acrylic resin composition, a sheet formed from the (meth)acrylic resin composition, and a laminate containing the sheet.

For the purpose of improving the surface hardness of the (meth)acrylic resin composition molded article and improving the solvent resistance and impact strength of the molded article, for example, a (meth)acrylic resin composition is blended with a fluororesin. An aspect is known (see Patent Document 1).

Moreover, for the purpose of improving the antistatic properties of the (meth)acrylic resin composition, there is known an aspect in which a glycerin monofatty acid ester is added to the (meth)acrylic resin composition (see Patent Document 2).

JP 2013-32513 A JP-A-5-239305

Due to the recent spread of new coronavirus infections, it is desired to impart antiviral properties to devices and instruments that may come into contact with the human body, and molded products made from (meth)acrylic resin compositions are expected to come into contact with the human body. The same applies to devices, instruments, etc. included as members in a manner to do so, for example.

However, in the (meth)acrylic resin composition and the molded article thereof according to the above-mentioned patent document, for example, no consideration is given to imparting antiviral properties to the new coronavirus, and even if the antiviral properties cannot be exhibited, Even so, for example, from the viewpoint of preventing infection with the new coronavirus, the surface treatment with ethanol (alcohol disinfection treatment), which is recommended for processing equipment and instruments, may cause the equipment and instruments to lose their antiviral properties. In some cases, the film is cracked, and furthermore, the transparency and antistatic properties are lost.

The present inventors have made intensive studies to solve the above problems, and found that by using a (meth)acrylic resin composition containing predetermined amounts of a (meth)acrylic resin, a vinylidene fluoride resin, and a glycerin fatty acid ester, , found that the above problems can be solved, and completed the present invention.

That is, the present invention provides the following [1] to [6].
[1] A (meth)acrylic resin composition containing a (meth)acrylic resin, a vinylidene fluoride resin, and a glycerin fatty acid ester,
The glycerin fatty acid ester is a glycerin fatty acid ester having an HLB value in the range of 5 or more and 12 or less,
In the (meth)acrylic resin composition, the content of the (meth)acrylic resin is 40% by mass or more when the total content of the (meth)acrylic resin, the vinylidene fluoride resin and the glycerin fatty acid ester is 100% by mass. is in the range of 84% by mass or less,
The content of the vinylidene fluoride resin is in the range of 15% by mass or more and 50% by mass or less,
A (meth)acrylic resin composition having a glycerin fatty acid ester content of 1% by mass or more and 10% by mass or less.
[2] The (meth)acrylic resin composition according to [1], wherein the glycerin fatty acid ester is a glycerin saturated fatty acid ester.
[3] A shaped material obtained by molding the (meth)acrylic resin composition according to [1] or [2].
[4] The formed material according to [3], which is a sheet obtained by molding the (meth)acrylic resin composition.
[5] A laminated sheet comprising one or more layers of the sheet according to [4].
[6] Further comprising a base material layer, the layer of the (meth)acrylic resin composition is provided on both the first main surface and the second main surface facing each other in the thickness direction of the base material layer. The laminated sheet according to [5], which is provided so as to sandwich the material layer.

According to the present invention, the molded body of the (meth)acrylic resin composition can maintain antiviral properties against the new coronavirus, for example, even by surface treatment with ethanol, and thus can maintain transparency. Furthermore, it is possible to provide a (meth)acrylic resin composition that can suppress the generation of static electricity and the adhesion of dust due to the generation of static electricity.

Embodiments of the present invention will be specifically described below. In addition, the present invention is not limited by the following description. The embodiments described below can be modified as appropriate without departing from the gist of the present invention.

The (meth)acrylic resin composition according to the present embodiment is a (meth)acrylic resin composition containing a (meth)acrylic resin, a vinylidene fluoride resin, and a glycerin fatty acid ester, wherein the glycerin fatty acid ester has an HLB value is a glycerin fatty acid ester in the range of 5 or more and 12 or less, and the total content of the (meth)acrylic resin, the vinylidene fluoride resin and the glycerin fatty acid ester in the (meth)acrylic resin composition is 100% by mass In addition, the content of the (meth)acrylic resin is in the range of 40% by mass to 84% by mass, the content of the vinylidene fluoride resin is in the range of 15% by mass to 50% by mass, and the glycerin fatty acid ester is contained. A (meth)acrylic resin composition having an amount in the range of 1% by mass or more and 10% by mass or less.

First, components that can be contained in the (meth)acrylic resin composition of the present embodiment will be specifically described.

<(Meth) acrylic resin>
Examples of (meth)acrylic resins that can be used in the (meth)acrylic resin composition of the present embodiment include homopolymers of (meth)acrylic monomers such as (meth)acrylic acid esters and (meth)acrylonitrile, or two types of Examples include copolymers of the above monomers, copolymers of (meth)acrylic monomers and other monomers, and the like.

In this specification, the term "(meth)acryl" means "acryl" or "methacryl".

As the (meth)acrylic resin, it is preferable to use a methacrylic resin because it has excellent hardness, weather resistance, and transparency. A methacrylic resin is a polymer obtained by polymerizing a monomer mainly composed of a methacrylate (alkyl methacrylate).

(Meth)acrylic resins include, for example, a homopolymer (polyalkyl methacrylate) of methacrylic acid ester as a monomer, a copolymer of methacrylic acid ester, and 50% by mass or more of methacrylic acid ester and 50% by mass or less. and copolymers with monomers other than methacrylic acid esters.

When the (meth)acrylic resin is a copolymer of a methacrylic acid ester and a monomer other than the methacrylic acid ester, the methacrylic acid ester is 70% by mass or more with respect to 100% by mass of the total amount of the monomers. Preferably, the monomer other than the methacrylic acid ester is 30% by mass or less, the methacrylic acid ester is 90% by mass or more, and the monomer other than the methacrylic acid ester is 10% by mass or less. is more preferable.

Examples of monomers other than methacrylic acid esters include acrylic acid esters and monofunctional monomers having one polymerizable carbon-carbon double bond in the molecule.

Examples of such monofunctional monomers include styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene; alkenyl cyanides such as acrylonitrile and methacrylonitrile; acrylic acid; methacrylic acid; maleic anhydride; ; N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide and methylmaleimide. A lactone ring structure, a glutaric anhydride structure, or a glutarimide structure may be introduced into the main chain (main skeleton) of the (meth)acrylic resin from the viewpoint of improving heat resistance.

More specifically, the (meth)acrylic resin is preferably a (meth)acrylic resin that satisfies the following condition (a1) or condition (a2).
(a1) a homopolymer of methyl methacrylate (a2) 50 to 99.9% by mass of structural units derived from methyl methacrylate and at least one derived from a (meth)acrylic acid ester represented by the following formula (1) A copolymer containing 0.1 to 50% by mass of two structural units

In the above formula (1), R ₁ represents a hydrogen atom or a methyl group, and when R 1 is a hydrogen atom, R ₂ represents an alkyl group _having 1 to 8 carbon atoms, and R ₁ is a methyl group. In some cases R ₂ represents an alkyl group of 2 to 8 carbon atoms.

In the condition (a2), the total amount of the structural unit derived from methyl methacrylate and at least one structural unit derived from the (meth)acrylic acid ester represented by the formula (1) is 100% by mass. Preferably.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ₂ when R ₁ is a hydrogen atom in the above formula (1) include methyl group, ethyl group, propyl group, isopropyl group and butyl group. , sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group. In the above formula (1), when R ₁ is a methyl group, examples of the alkyl group having 2 to 8 carbon atoms represented by R ₂ include an ethyl group, a propyl group, an isopropyl group, a butyl group, sec- Examples include butyl, tert-butyl, pentyl, hexyl, heptyl and octyl groups.

The (meth)acrylic acid ester represented by the formula (1) is preferably methyl acrylate or ethyl acrylate, more preferably methyl acrylate.

In the present embodiment, the (meth)acrylic resin has a melt mass flow rate (MFR) at 230° C. measured under a load of 3.8 kg according to a method in accordance with JIS K 7210, which is usually 0.1 to 30 g/10 minutes, From the viewpoint of improving the strength of a molded product obtained by molding the (meth)acrylic resin composition and improving its moldability, it is preferably 0.2 to 20 g/10 minutes, more preferably 0.5 to 15 g/ 10 minutes.

In the present embodiment, the (meth)acrylic resin has a weight average molecular weight (Mw) determined by GPC measurement, for example, improves transparency when exposed to conditions of 60 ° C. and 90% relative humidity, and moldability is preferably from 30,000 to 300,000, more preferably from 40,000 to 250,000, even more preferably from 50,000 to 200,000, from the viewpoint of improving the

In the present embodiment, from the viewpoint of improving heat resistance, the (meth)acrylic resin preferably has a Vicat softening temperature (VST) of 90° C. or higher, measured according to a method conforming to JIS K 7206, and preferably 100° C. or higher. and more preferably 102° C. or higher. The VST of the (meth)acrylic resin can be appropriately set by adjusting the types and ratios of the monomers and the molecular weight of the (meth)acrylic resin.

The (meth)acrylic resin can be prepared (synthesized) by polymerizing the monomers already described by any suitable conventionally known method such as suspension polymerization or bulk polymerization. In the preparation, properties such as MFR, Mw, and VST of the (meth)acrylic resin can be adjusted within preferred ranges by further adding, for example, a conventionally known suitable chain transfer agent. The amount of the chain transfer agent to be added can be appropriately determined according to the type and ratio of the selected monomers and the required properties.

<Vinylidene fluoride resin>
In the present embodiment, vinylidene fluoride resins that can be used in the (meth)acrylic resin composition include, for example, vinylidene fluoride homopolymers and vinylidene fluoride copolymers. The copolymer of vinylidene fluoride includes at least one monomer selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene, and fluorinated A polymer obtained by copolymerizing with vinylidene can be mentioned. The vinylidene fluoride resin is preferably a vinylidene fluoride homopolymer (polyvinylidene fluoride) from the viewpoint of improving the transparency of the molded article.

In the present embodiment, the vinylidene fluoride resin usually has a melt mass flow rate (MFR) of 0.1 to 30 g/10 minutes at 230° C. measured under a load of 3.8 kg according to the method in accordance with JIS K 7210. It is preferably 0.2 to 25 g/10 minutes, more preferably 0.5 to 20 g/10 minutes, from the viewpoint of suppressing deterioration of transparency due to long-term use of the molded article and improving moldability. .

In this embodiment, the vinylidene fluoride resin has a weight average molecular weight (Mw) determined by GPC measurement, for example, improves the transparency of the molded product when exposed to conditions of 60 ° C. and a relative humidity of 90%, From the viewpoint of improving moldability, it is preferably from 100,000 to 500,000, more preferably from 150,000 to 450,000, even more preferably from 200,000 to 450,000.

Vinylidene fluoride resins are industrially produced by a suspension polymerization method or an emulsion polymerization method. The suspension polymerization method can be carried out by using water as a medium, dispersing the monomers as droplets in the medium using a dispersant, and polymerizing the organic peroxide dissolved in the monomers as a polymerization initiator. A granular polymer of 100 to 300 μm can be obtained. Compared with polymers produced by emulsion polymerization, polymers produced by suspension polymerization can be produced easily, are excellent in powder handling properties, and are superior to polymers produced by emulsion polymerization. It is preferable because it does not contain an emulsifier containing an alkali metal or a salting-out agent, unlike coalescence.

<Glycerol fatty acid ester>
Glycerin fatty acid esters are known to have antiviral properties that can inactivate the novel coronavirus.

In the present embodiment, the glycerin fatty acid ester has a function of exhibiting antiviral properties particularly against the novel coronavirus, and furthermore, by exuding (bleeding) on the surface of the molded body and covering the surface, It has the function of suppressing the generation of static electricity and the adhesion of dust.

In this embodiment, the glycerin fatty acid ester is a glycerin fatty acid ester having an HLB value in the range of 5 or more and 12 or less. The HLB value bleeds the glycerin fatty acid ester to the surface, and even if it is wiped off, the glycerin fatty acid ester will bleed again. is preferably 5.4 or more, and preferably 9.4 or less, from the viewpoint of recovery. The HLB value is preferably in the range of 5 or more and 9.4 or less, or in the range of 5.4 or more and 12 or less, and more preferably in the range of 5.4 or more and 9.4 or less.

Here, the HLB (Hydrophilic Lipophilic Balance) value is a parameter that can take values from 0 to 20, and the closer to 0, the higher the lipophilicity (hydrophobicity), and the closer to 20, the higher the hydrophilicity. is a parameter that represents A compound such as paraffin having only a hydrophobic group without a hydrophilic group has an HLB value of 0, and a compound having only a hydrophilic group without a hydrophobic group such as polyethylene glycol has an HLB value. is 20, and compounds having both hydrophilic and hydrophobic groups in one molecule will have a value between 1 and 20. Therefore, the greater the hydrophilicity of the hydrophilic group relative to the hydrophobicity of the hydrophobic group in the molecule, the higher the HLB value and the higher the water solubility. Therefore, the smaller the hydrophilicity of the hydrophilic group, the smaller the HLB value and the lower the water solubility.

The HLB value of a given compound (molecule) can be calculated, for example, by Griffin's method using the following formula (2).

HLB value = 20 × sum of chemical formula weights of hydrophilic moieties/sum of chemical formula weights of hydrophobic moieties (2)

In this embodiment, the number of carbon atoms in the alkyl chain of the glycerin fatty acid ester is not particularly limited. Specific examples include caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, and oleic acid. Moreover, as fatty acid ester which comprises a glycerin fatty acid ester, a mono-fatty-acid ester, a di-fatty-acid ester, and a tri-fatty-acid ester are mentioned, for example. Among these, the fatty acid ester is preferably mono-fatty acid ester or di-fatty acid ester.

Glycerin that can constitute the glycerin fatty acid ester that can be used in the present embodiment includes, for example, monoglycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, and decaglycerin. Among these, glycerin that can constitute a glycerin fatty acid ester is preferably monoglycerin, diglycerin, or decaglycerin, and more preferably diglycerin.

Specific examples of glycerin fatty acid esters include monoglycerin monocaprylate (HLB value 7.0), monoglycerin monocaprate (HLB value 6.8), monoglycerin monolaurate (HLB value 5.0). 4), monoglycerin monomyristate, diglycerin monocaprylate, diglycerin monocaprate, diglycerin monolaurate (HLB value 9.4), diglycerin monomyristate, triglycerin monocaprylate, triglycerin monocaprate, triglycerin monolaurate, triglycerin monomyristate, tetraglycerin monocaprylate, tetraglycerin monocaprate, tetraglycerin monolaurate, tetraglycerin monomyristate, pentaglycerin monocaprylate, pentaglycerin monocaprate , pentaglycerin monolaurate, pentaglycerin monomyristate, decaglycerin monooleate (decaglycerin oleate) (HLB value 12), among these, monoglycerin monocaprate (HLB value 6.8), Glycerin saturated fatty acid esters such as monoglycerin monolaurate (HLB value 5.4) and diglycerin monolaurate (HLB value 9.4) are preferable. .4) is more preferably used.

As for the HLB value of the glycerin fatty acid ester, for example, values disclosed in conventionally known documents can be referred to and applied. Moreover, as a glycerin fatty acid ester, you may obtain and use a commercial product, for example.

<(Meth) acrylic resin composition>
(1) (Meth)acrylic resin In the (meth)acrylic resin composition of the present embodiment, the content of the (meth)acrylic resin is the content of the (meth)acrylic resin, the vinylidene fluoride resin and the glycerol fatty acid ester already described. When the total amount is 100% by mass, it is usually more than 20% by mass and less than 85% by mass, and is effective in maintaining antiviral properties, maintaining transparency, generating static electricity, and adhering dust. From the viewpoint of suppression, the range may be 40% by mass or more and 84% by mass or less, preferably 42% by mass or more, more preferably 45% by mass or more, and 47.5% by mass or more. is more preferably 55% by mass or less, more preferably 70% by mass or less, and particularly from the viewpoint of improving transparency, the range is preferably 42% by mass or more and 84% by mass or less, It is more preferably in the range of 45% by mass or more and 84% by mass or less, more preferably in the range of 42% by mass or more and 70% by mass or less, and particularly in the range of 47.5% by mass or more and 70% by mass or less. preferable.

(2) Vinylidene fluoride resin In the (meth)acrylic resin composition of the present embodiment, the content of the vinylidene fluoride resin is equal to the content of the (meth)acrylic resin, the vinylidene fluoride resin and the glycerin fatty acid ester already described. When the total is 100% by mass, it is usually more than 10% by mass and less than 75% by mass, and maintains antiviral properties, maintains transparency, generates static electricity, and effectively suppresses adhesion of dust. In particular, from the viewpoint of ensuring transparency, the range may be 15% by mass or more and 50% by mass or less, preferably 25% by mass or more, preferably 50% by mass or less, and 40% by mass or less. Especially from the viewpoint of improving transparency, it is preferably in the range of 25% by mass or more and 50% by mass or less, and more preferably in the range of 40% by mass or more and 50% by mass or less.

(3) Glycerin fatty acid ester In the (meth)acrylic resin composition of the present embodiment, the content of glycerin fatty acid ester is the total content of the already described (meth)acrylic resin, vinylidene fluoride resin and glycerin fatty acid ester. When it is 100% by mass, it is usually more than 0.5% by mass and less than 15% by mass, and maintains antiviral properties, maintains transparency, and effectively suppresses the generation of static electricity and adhesion of dust. In particular, from the viewpoint of ensuring transparency, antiviral properties due to rebleeding, generation of static electricity, and restoration of effective suppression of adhesion of dust, the content may be in the range of 1% by mass or more and 10% by mass or less. It is preferably 5% by mass or more, preferably 8% by mass or less, more preferably 5% by mass or less, and particularly from the viewpoint of maintaining effective antiviral properties, 2.5% by mass or more. It is preferable to make it into the range of 5.0 mass % or less.

In the (meth)acrylic resin composition of the present embodiment, by blending the (meth)acrylic resin, the vinylidene fluoride resin and the glycerin fatty acid ester in the above proportions, antiviral properties and the transparency of the cast material, which is a molded product, are achieved. Furthermore, the generation of static electricity on the surface of the shaped material and the adhesion of dust can be effectively suppressed. Even if the glycerin fatty acid ester bleeding onto the surface of the shaped material is wiped off by the disinfection treatment, the glycerin fatty acid ester can be rebleed on the surface, and antiviral properties, static electricity generation, and eventually Dust adhesion can be effectively suppressed, and these properties can be maintained for a predetermined period of time.

The amount of other resins that can be contained in the (meth)acrylic resin composition of the present embodiment is preferably 20% by mass or less with respect to the total amount (100% by mass) of the (meth)acrylic resin composition, It is more preferably 10% by mass or less, and even more preferably 5% by mass or less.

Other resins that may be contained in the (meth)acrylic resin composition of the present embodiment include, for example, polycarbonate resins, polyamide resins, acrylonitrile-styrene copolymers, methyl methacrylate-styrene copolymers, and polyethylene terephthalate. .

(4) Other Components The (meth)acrylic resin composition of the present embodiment further contains other components that can be generally used in methacrylic resin compositions, provided that the effects of the present invention are not impaired. You can

Other components that the (meth)acrylic resin composition of the present embodiment may contain include, for example, crosslinked rubber particles, ultraviolet absorbers, slip agents, antioxidants, release agents, and antistatic agents.

The crosslinked rubber particles that are other components, for example, have at least a core portion and a coating layer that covers the core portion, and at least one of the core portion and the coating layer has a carbon-carbon unsaturated bond. A multi-layered rubber particle formed from a material having two or more structural units derived from a polyfunctional monomer may be mentioned.

Examples of UV absorbers that are other components include benzophenone UV absorbers, cyanoacrylate UV absorbers, benzotriazole UV absorbers, malonic acid ester UV absorbers, and oxalanilide UV absorbers. be done.

Examples of slip agents, which are other components, include silicone oils and polysiloxane compounds.

Antioxidants that are other components include, for example, phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants.

Other components of the mold release agent include, for example, higher fatty acid esters, higher fatty alcohols, higher fatty acids, higher fatty acid amides, higher fatty acid metal salts, and fatty acid derivatives different from the "glycerin fatty acid ester" already described. .

Examples of other components, antistatic agents, include conductive inorganic particles, tertiary amines, quaternary ammonium salts, cationic acrylic acid ester derivatives, and cationic vinyl ether derivatives.

<Method for producing (meth)acrylic resin composition>
The (meth)acrylic resin composition of the present embodiment can be produced by mixing the (meth)acrylic resin, the vinylidene fluoride resin, the glycerin fatty acid ester, and other desired components, which have already been described, with any conventionally known suitable equipment and conditions. It can be manufactured (prepared) by performing a kneading step by.

In the present embodiment, the temperature conditions in the (melting) kneading step are not particularly limited. The temperature conditions can be arbitrary and suitable conditions in consideration of the selected components, their amounts, properties, and the like. In the melt-kneading step, for example, the temperature from the raw material inlet to the outlet of the extruder may be 180°C to 260°C.

As a device that can be used in the kneading step, any suitable conventionally known mixer or kneader can be used. Specific examples of such devices include single-screw kneaders, twin-screw kneaders, multi-screw extruders, Henschel mixers, Banbury mixers, kneaders, and roll mills. Moreover, when it is necessary to increase the rotational speed in the kneading step, for example, a high shear processing device may be used.

<Materials>
The (meth)acrylic resin composition of the present embodiment can be formed into a molded material molded into a desired shape by molding by any suitable conventional molding method (for the manufacturing method of the molded material, described later).

According to the molded material of the present embodiment, the glycerin fatty acid ester already described bleeds on the surface without reducing transparency, and the glycerin fatty acid ester exhibits antiviral properties as an active ingredient, and furthermore, can effectively suppress the generation of static electricity and the adhesion of dust on the surface of the cast material, and even if the glycerin fatty acid ester is wiped off, it can rebleed the glycerin fatty acid ester, It can be used as a molding material capable of recovering (maintaining) the effect of suppressing the generation of virality and static electricity, as well as the adhesion of dust.

Here, forged materials refer to parts, members, and final products themselves that are given a predetermined shape by applying predetermined heat and force to materials such as resin compositions, rubber, glass, and metals. Say. That is, the molded material having antiviral properties of the present embodiment is a molded article formed into a predetermined shape by molding the (meth)acrylic resin composition described above.

In this embodiment, the shape, thickness, and other size of the preform that can be manufactured are not particularly limited. In the present embodiment, the preform is preferably a sheet (layered body, plate-shaped body) obtained by molding the (meth)acrylic resin composition described above.

Further, in the present embodiment, a laminated sheet including one or more sheets formed by molding the (meth)acrylic resin composition described above as a layer of the (meth)acrylic resin composition can also be used. That is, the cast material of the present embodiment includes a laminated sheet (laminate) including a layer containing the (meth)acrylic resin composition described above.

In addition to high transparency, the cast material obtained by molding the (meth)acrylic resin composition of the present embodiment has antiviral properties, especially against the new coronavirus, and the generation of static electricity on the surface of the cast material and the adhesion of dust. can be effectively suppressed. Therefore, it can be suitably used as a device, instrument, etc. that can come into contact with the human body, or as a material included in the device, instrument, or the like.

Since the molded material obtained by molding the (meth)acrylic resin composition of the present embodiment has the properties as already described, specifically, Screens and partitions (which can be placed on desks) to separate attendees who are adjacent or facing each other in meetings, etc., cover members for covering product samples in vending machines, cover members for lights, etc. can be suitably used as a display panel member such as a protective sheet located on the outermost surface of a touch sensor panel, or as a meter panel member for vehicles such as automobiles and motorcycles.

(1) Sheet The thickness of the sheet, which is the material formed by molding the (meth)acrylic resin composition of the present embodiment, may be appropriately selected according to the application, and is not particularly limited. In this embodiment, the thickness of the sheet is preferably 100 to 4000 μm, more preferably 200 to 3000 μm, when applied to screens and partitions, for example.

(2) Laminated sheet In the present embodiment, the laminated sheet includes one or more sheets obtained by molding the (meth)acrylic resin composition described above as a layer of the (meth)acrylic resin composition. The layer of the (meth)acrylic resin composition is preferably provided so as to cover at least the surface expected to come into contact with the human body.

In the present embodiment, the laminated sheet further includes a substrate layer from the viewpoint of improving hardness and strength, and the layer of the (meth)acrylic resin composition faces the thickness direction of the substrate layer. It is preferable to have a configuration in which the substrate layers are provided on both sides of the first main surface and the second main surface so as to sandwich the base material layer. The substrate layer may include not only one layer but also two or more layers.

Here, the thickness of the base material layer can be any suitable thickness in consideration of the use of the laminated sheet. When the laminated sheet is applied to, for example, a screen or a partition, the thickness of the base layer is preferably 500-4000 μm, more preferably 1000-3000 μm, from the viewpoint of shape retention.

The material of the base material layer is not particularly limited and may be selected from conventionally known suitable materials depending on the application of the laminated sheet. Examples of the material of the base material layer include (meth)acrylic resin, styrene resin, MS resin, polycarbonate resin and the like. In particular, the sheet ((meth)acrylic resin composition layer) of the present embodiment has high transparency, and when combined with a highly transparent base material layer, the transparency of the entire laminated sheet can be increased. It is preferable to use a transparent material as the material of .

For example, when the laminated sheet is a screen or partition that is expected to be used face-to-face, and transparency (visible light transmittance) is particularly required, the material of the base layer is the (meta ) It is preferably a (meth)acrylic resin composition which may have a different composition and compounding ratio from the acrylic resin composition. Here, from the viewpoint of ensuring transparency, the material of the substrate layer is preferably composed only of (meth)acrylic resin, and the (meth)acrylic resin composition further includes other resins such as vinylidene fluoride resin. It can be a thing.

<Manufacturing method of raw materials>
The method for manufacturing the cast material of the present embodiment is not particularly limited. Examples of the method for producing the cast material of the present embodiment include a method of molding the already-described (meth)acrylic resin composition using a conventionally known arbitrary suitable molding machine.

Extrusion molding and injection molding are examples of methods for manufacturing the cast material of the present embodiment. In the case of making the cast material into a more complicated shape, for example, an injection molding machine is used as the molding machine, and the (meth)acrylic resin composition is injected into the mold of the molding machine and molded. A molding method may be used.

In the case of forming the already described sheet or laminated sheet, it is preferable to use an extrusion molding method. In particular, when producing a laminated sheet in which the material of the substrate layer is a resin composition to which an extrusion molding method can be applied, typified by a (meth)acrylic resin composition, the substrate layer and the (meth)acrylic of the present embodiment A layer of a (meth)acrylic resin composition containing a resin composition can be molded at the same time, and a laminated sheet can be integrally produced more easily.

Hereinafter, the manufacturing method of the cast material of the present embodiment will be described by taking the manufacturing method by the extrusion molding method as an example.

The method for manufacturing the cast material of the present embodiment includes a step of preparing a (meth)acrylic resin composition and a step of extruding the prepared (meth)acrylic resin composition into a cast material. Each step will be specifically described below.

(1) Step of preparing a (meth)acrylic resin composition This step is a step of preparing a (meth)acrylic resin composition to be supplied to an extruder.

In the present embodiment, the properties of the methacrylic resin composition supplied to the extruder are not particularly limited. The shape, size, and the like of the (meth)acrylic resin composition to be supplied to the extruder may be set within an arbitrary and suitable range in consideration of the extruder to be used, applicable conditions, and the like.

(2) A step of extruding a (meth)acrylic resin composition into a cast material. be.

Specifically, the sheet, which is an example of the cast material of the present embodiment, is manufactured by extruding a molten (meth)acrylic resin composition from a die of an extruder and molding it with a die lip according to a conventional method. can do.

A laminated sheet that is an example of the formed material of the present embodiment, for example, the sheet as a layer of a (meth)acrylic resin composition, the first main surface facing the thickness direction of the base material layer and Laminated sheets having a two-kind three-layer structure (layer of (meth)acrylic resin composition/base layer/(meth)acrylic resin) provided on both sides of the second main surface so as to sandwich the base layer A laminated sheet in which layers of the composition are laminated in order) can be produced, for example, as follows.

First, a melt of the (meth)acrylic resin composition of the present embodiment and a melt of the resin composition that is the material of the substrate layer are prepared.

Next, for example, using an extruder equipped with a multi-manifold die, the melted resin composition that is the material of the base layer is extruded from the middle die lip, and at the same time, the upper die lip and the lower die lip are melted. The (meth)acrylic resin composition of the present embodiment is extruded, and the extruded molded body is, if necessary, cooled using a conventionally known arbitrary suitable cooling roll, or other rolls such as a conveying roll The (meth)acrylic of the present embodiment is sandwiched between the first main surface and the second main surface of the base material layer molded in the middle stage, such as by further molding using A laminated sheet, which is a laminate having a two-kind three-layer structure, including a (meth)acrylic resin composition layer, which is a resin composition layer (sheet), can be produced.

In producing the laminated sheet of the present embodiment, the temperature conditions for molding the layer of the (meth)acrylic resin composition by an extrusion molding method are the composition of the (meth)acrylic resin composition, the required (meth) It can be appropriately selected in consideration of the thickness of the layer of the acrylic resin composition. The temperature conditions for molding the layer of the (meth)acrylic resin composition are, for example, preferably 180 to 300°C, more preferably 200 to 290°C, and further preferably 220 to 280°C. preferable. The temperature is the temperature of the melt of the (meth)acrylic resin composition at the die lip of the die (or immediately after extrusion).

The melt of the resin composition for forming the base material layer can be extruded from a die in a heated state if necessary. In the production of the laminated sheet of the present embodiment, the temperature conditions for molding the base layer by extrusion molding include the components of the resin composition as the material, the blending ratio, the required thickness of the base layer, and the like. can be selected as appropriate. The temperature conditions for molding the substrate layer are preferably, for example, 180 to 300° C., more preferably 200 to 290° C., when the substrate layer is formed from a (meth)acrylic resin composition. More preferably, the temperature is 220 to 280°C. The temperature is the temperature of the molten resin composition at the die lip of the die (or immediately after extrusion).

The thickness of the (meth)acrylic resin composition layer in the laminated sheet of the present embodiment is not particularly limited. The thickness of the (meth)acrylic resin composition layer is transparent, antiviral, effectively suppresses the generation of static electricity and adhesion of dust, and is antiviral by rebleeding, generation of static electricity and adhesion of dust. From the viewpoint of recovery of effective suppression of , it is preferably 0.05 mm or more and 1.0 mm or less, and more preferably 0.1 mm or more and 0.5 mm or less. When the laminated sheet contains two or more layers of the (meth)acrylic resin composition, the thickness of the two or more (meth)acrylic resin composition layers may be the same or different. .

The thickness of the base material layer in the laminated sheet of this embodiment is not particularly limited. The thickness of the base material layer is preferably 0.05 mm or more and 4 mm or less, more preferably 0.1 mm or more and 3 mm or less, from the viewpoint of securing the hardness and strength of the laminated sheet.

<Evaluation method>
(1) Haze and its measuring method The layer of the (meth)acrylic resin composition contained in the sheet and laminated sheet of the present embodiment has high transparency. Haze (Haze 2 mmt (%)) evaluated as a measure of transparency can be measured in accordance with JIS K 7136 (ISO 14782, which corresponds to Plastics-Determination of haze for transparent materials). A specific description will be given below.

First, the haze is 0.044 rad (2.5 °) Refers to the percentage of transmitted light deviated above.

In this embodiment, the haze can be measured by any suitable conventionally known device (eg, haze meter HR-100 (manufactured by Murakami Color Research Laboratory)). Devices for measuring haze include, for example, devices with a stable light source, connecting optics, an integrating sphere with an aperture, and a photometer. The photometer preferably consists of a photodetector, a signal processor and a display or recorder.

A plurality of cut test pieces are usually used for haze measurement. The size of the specimen is not limited provided it is large enough to cover the entrance and compensation apertures of the integrating sphere.

First, the specimens are conditioned according to ISO 291 at a temperature of (23±2)° C. and a relative humidity of (50±10)% for 15 minutes prior to haze measurement.

Next, the device used for measurement is installed in an atmosphere maintained at a temperature of (23 ± 2) ° C. and a relative humidity of (50 ± 10)% as necessary, and a sufficient time has passed before measurement. Allow to reach thermal equilibrium.

Next, the test piece is placed in an apparatus, the luminous flux of the incident light transmitted through the test piece is observed, and the haze (%) is calculated by the following formula (3).

Haze = [(τ4/τ2) - τ3 (τ2/τ1)] × 100 (3)

In the above formula (3),
τ1 represents the luminous flux of incident light,
τ2 represents the total luminous flux transmitted through the test piece,
τ represents the luminous flux diffused in the device,
τ4 represents the luminous flux spread by the device and specimen.

(2) Surface resistivity and its measuring method The layer of the (meth)acrylic resin composition contained in the sheet and laminated sheet of the present embodiment has glycerin fatty acid ester, which is an active ingredient for antiviral properties, on the entire surface. Due to bleeding, the surface resistivity (Ω / sq) is reduced to at least less than 1.0E + 14 Ω / sq, and the bleeding glycerin fatty acid ester is wiped off, increasing the surface resistivity. Even if the surface resistivity is lost, the glycerin fatty acid ester bleeds again to reduce the surface resistivity. As a result, it is possible to maintain the antiviral properties and the effect of effectively suppressing the generation of static electricity on the surface of the shaped material and thus the adhesion of dust for a predetermined period of time.

In this embodiment, the surface resistivity is measured using a resistivity meter (e.g., Hiresta UP MCP-HT-450 manufactured by Mitsubishi Chemical Analytech Co., Ltd.), which is a conventionally known suitable measuring device. It can be measured according to K6911.

In measuring the surface resistivity, for example, after adjusting the condition by leaving it under the conditions of 23 ° C. and 50% RH for 24 hours, using the apparatus already described, by a method in accordance with JIS K 6911. measurements can be made.

Examples of the present invention will be specifically described below. The invention is not limited by the examples described below.

Glycerin fatty acid esters (C-1) to (C-5) used in Examples and Comparative Examples described later and their HLB values are as follows. All glycerin fatty acid esters were commercially available from Riken Vitamin Co., Ltd. and used.
C-1: DL-100 diglycerin monolaurate HLB value 9.4
C-2: M-300 glycerin monolaurate HLB value 5.4
C-3: J-0381V Decaglycerin oleate HLB value 12
C-4: H-100 glycerin stearate HLB value 4.3
C-5: J-0021 Decaglycerin laurate HLB value 15.5

<Example 1>
[Preparation of (meth)acrylic resin composition]
47.5 parts by mass of polymethyl methacrylate (PMMA) (Sumipex LG2, manufactured by Sumitomo Chemical Co., Ltd.), which is a (meth)acrylic resin, and polyvinylidene fluoride (PVDF) (KF Polymer #), which is a vinylidene fluoride resin 1300 Kureha Co., Ltd.) 50 parts by mass and 2.5 parts by mass of diglycerin monolaurate (DL-100 Riken Vitamin Co., Ltd.) were mixed using an ME type Laboplastomill (Toyo Seiki Co., Ltd.). and kneaded for 5 minutes at a rotation speed of 80 rpm to obtain a (meth)acrylic resin composition. Table 1 shows the composition (% by mass) of the (meth)acrylic resin composition.

[Production of compact (plate)]
The (meth)acrylic resin composition obtained as described above was placed in a frame mold with a thickness of 2 mm and preheated at 210° C. for 5 minutes. Next, press at a pressure of 2 MPa for 3 minutes, press at a pressure of 12 MPa for 1 minute, and then cool at room temperature at a pressure of 2 MPa for 1 minute to form a flat molded body (plate) (thickness: 2 mm). Obtained.

[Measurement of haze]
"Haze (Haze 2 mmt (%))" was measured by a method based on JIS K 7136 using a haze meter HR-100 (manufactured by Murakami Color Laboratory). The results are shown in Table 1 below.

[Measurement of surface resistivity]
"Surface resistivity (Ω/sq)" was measured according to JIS K 6911 using a resistivity meter (Hiresta UP MCP-HT-450, manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

A sample obtained by cutting the plate manufactured as described above into a size of 50 mm×50 mm was left under conditions of 23° C. and 50% RH for 24 hours. The surface resistivity of the plate was then measured.

The upper limit of the surface resistivity that can be measured by the above resistivity meter is 1.0E+14Ω/sq, and when the surface resistivity exceeds this numerical value, it will be regarded as "OVER".

[Measurement of surface resistivity immediately after wiping and 3 days after wiping]
The surface of the plate manufactured as described above was wiped (wiped) with Bencotton impregnated with special grade ethanol.

First, immediately after wiping, the surface resistivity of the wiped surface of the plate was measured. After wiping, the plate was left under conditions of 23° C. and 50% RH for 72 hours. The surface resistivity was then measured on the wiped surface of the plate.

<Examples 2 to 7>
The (meth)acrylic resin compositions of Examples 2 to 7 were prepared in the same manner as in Example 1 except that the composition was as shown in Table 1 below, and the haze was adjusted in the same manner as in Example 1. and surface resistivity were measured. The results are shown in Table 1 below.

<Comparative Examples 1 to 6>
(Meth)acrylic resin compositions according to Comparative Examples 1 to 6 were prepared in the same manner as in Example 1 except that the composition was as shown in Table 2 below, and the haze was adjusted in the same manner as in Example 1. and surface resistivity were measured. The results are shown in Table 2 below.

According to Examples 1 to 7, which satisfy the requirements of the present invention, the surface resistivity can be reduced without impairing the transparency, and as a result, the glycerin fatty acid ester bleeds onto the surface of the molded article. , antiviral properties, generation of static electricity, and ability to suppress adhesion of dust due to generation of static electricity.

In addition, according to Examples 1 to 7, which satisfy the requirements of the present invention, even if the glycerin fatty acid ester was wiped off from the surface of the molded product by alcohol disinfection treatment, the glycerin fatty acid ester was removed after at least 3 days. It was shown that rebleeding to the surface could restore the antiviral properties, the generation of static electricity, and the effect of suppressing the adhesion of dust due to the generation of static electricity.

On the other hand, according to Comparative Examples 1 to 6, which do not satisfy at least one of the requirements of the present invention, the surface resistivity by securing transparency, reducing surface resistivity (imparting antiviral properties) and/or rebleeding It was shown that recovery from the reduction of the antiviral activity (recovery of antiviral properties) was not possible.

Claims (6)

A (meth)acrylic resin composition containing a (meth)acrylic resin, a vinylidene fluoride resin, and a glycerin fatty acid ester,
The glycerin fatty acid ester is a glycerin fatty acid ester having an HLB value in the range of 5 or more and 12 or less,
In the (meth)acrylic resin composition, the content of the (meth)acrylic resin is 40% by mass or more when the total content of the (meth)acrylic resin, the vinylidene fluoride resin and the glycerin fatty acid ester is 100% by mass. is in the range of 84% by mass or less,
The content of the vinylidene fluoride resin is in the range of 15% by mass or more and 50% by mass or less,
A (meth)acrylic resin composition having a glycerin fatty acid ester content of 1% by mass or more and 10% by mass or less. The (meth)acrylic resin composition according to claim 1, wherein the glycerin fatty acid ester is a glycerin saturated fatty acid ester. A shaped material obtained by molding the (meth)acrylic resin composition according to claim 1 or 2. The formed material according to claim 3, which is a sheet obtained by molding the (meth)acrylic resin composition. A laminated sheet comprising one or more layers of the sheet according to claim 4 . Further comprising a substrate layer, the layer of the (meth)acrylic resin composition has the substrate layer on both the first main surface and the second main surface facing each other in the thickness direction of the substrate layer. The laminated sheet according to claim 5, which is provided so as to sandwich.