JP2007210309A - Functional sheet and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functional sheet which has a layer of an anckor coat on a thin layer being composed of an acrylic rubber reinforced composition and being superior in adhesivity and printability on the surface, and its manufacturing process. <P>SOLUTION: The functional sheet 1 has a thin layer 11 composed of an acrylic rubber reinforced resin composition, a crona-treated layer 12 formed on at least one of the surfaces of the thin layer 11 and an anckor coat layer 13 formed on the surface of the crona-treated layer 12. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a functional sheet excellent in whitening resistance, low shrinkage, and printability, and suitable for producing a printed sheet, a decorative sheet, and the like, and a method for producing the functional sheet.

  Conventionally, the walls of ceilings, kitchens, bathrooms, toilets, toilets, etc. in buildings such as houses are made up and the surfaces of various furniture, etc. are contaminated and scratched from the outside, as well as water, moisture, heat, mold, etc. The decorative sheet disposed for protecting the surface from the surface is widely used by printing various designs, patterns, characters, etc. on the surface of the base sheet. The surface of the base sheet is pretreated for the purpose of effectively producing a printed image, thereby imparting good printability. As a material for a base sheet such as a decorative sheet, a resin composition containing a vinyl chloride resin or the like, cardboard, or the like has been used (for example, Patent Document 1). However, an alternative to a resin composition containing an olefin resin such as polyethylene or polypropylene, an ABS resin, an AES resin, or the like has been studied against the background of environmental problems.

JP-A-9-277460

  The purpose of the present invention is to provide a functional sheet having an anchor coat layer on a thin body made of an acrylic rubber-reinforced resin composition, excellent adhesion of the anchor coat layer, excellent printability in the anchor coat layer, The object is to provide a functional sheet excellent in whitening resistance and low shrinkage and a method for producing the functional sheet.

The present invention is shown below.
1. A thin-walled body made of an acrylic rubber-reinforced resin composition, a corona-treated layer formed on at least one surface of the thin-walled body, and an anchor coat layer disposed on the surface of the corona-treated layer Functional sheet.
2. The acrylic rubber reinforced resin composition is obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber polymer having a volume average particle diameter of 60 to 500 nm. The rubber-reinforced vinyl resin (A1) or a mixture of the rubber-reinforced vinyl resin (A1) and a (co) polymer (A2) of a vinyl monomer and having a graft ratio of 20 2. The functional sheet according to 1 above, which comprises ˜170% acrylic rubber reinforced resin.
3. The acrylic rubber-reinforced resin composition contains a grafted acrylic rubbery polymer, and contains an acrylic rubber-reinforced resin containing a unit made of an aromatic vinyl compound and a unit made of a vinyl cyanide compound. The acrylic rubber-reinforced resin has a graft ratio of 20 to 170%, the grafted acrylic rubbery polymer has a number average particle size of 60 to 200 nm, and has an intrinsic viscosity of acetonitrile-soluble component. 0.4 to 0.8 dl / g, the amount of bound vinyl cyanide compound in the acetonitrile-soluble component is 3 to 40% by mass, and the amount of bound vinyl cyanide compound measured by liquid chromatography is 2. The functional sheet according to 1 above, wherein the standard deviation of distribution is 5 or less.
4). The functional sheet according to any one of 1 to 3 above, wherein the thickness is 30 to 500 μm.
5). 5. The thermal shrinkage rate (according to JIS K7133, state rough adjustment at a temperature of 80 ° C. for 30 minutes) is 1% or less in the vertical direction and 1% or less in the horizontal direction. Functional sheet.
6). The functional sheet according to any one of 1 to 5 above, wherein a wetting index (based on JIS K6768) on the surface of the corona-treated layer is 40 mN / m or more.
7). The anchor coat layer is a modified olefin composition, polyester composition, acrylic composition, polyurethane composition, isocyanate composition, polyethyleneimine composition, polyamide composition, maleic acid composition, acetic acid. 7. The functional sheet according to any one of 1 to 6 above, comprising at least one selected from a vinyl composition, a polyvinyl butyral composition, a natural rubber composition, and a synthetic rubber composition.
8). 8. The functional sheet according to any one of 1 to 7, wherein the anchor coat layer has a thickness of 0.01 to 10 μm.
9. The functional sheet according to any one of 1 to 8 above, wherein the surface of the anchor coat layer has a matte property.
10. A method in which the matte property includes at least one kind of fine particles selected from a polymer and an inorganic compound in the anchor coat layer, or a method in which a matte layer containing the fine particles is provided on the surface of the anchor coat layer, Or the functional sheet | seat of said 9 obtained by the method of combining this method.
11. 11. The functional sheet according to 10 above, wherein the matte layer has a thickness of 0.5 to 10 μm.
12 9. The method for producing a functional sheet according to any one of 1 to 8 above, wherein corona treatment is performed on at least one surface of a thin-walled body made of an acrylic rubber-reinforced resin composition to form a corona treatment layer. Corona treatment step, and on the surface of the corona treatment layer, water-based and modified olefin composition, polyester composition, acrylic composition, polyurethane composition, isocyanate composition, polyethyleneimine composition At least one anchor coating composition selected from polyamide compositions, maleic acid compositions, vinyl acetate compositions, polyvinyl butyral compositions, natural rubber compositions and synthetic rubber compositions And a process for producing a functional sheet.

According to the functional sheet of the present invention, a thin-walled body made of an acrylic rubber-reinforced resin composition, a corona-treated layer formed on at least one surface of the thin-walled body, and disposed on the surface of the corona-treated layer. Since the anchor coat layer is provided, the adhesion of the anchor coat layer on the surface of the corona-treated layer is excellent, and the printability of the anchor coat layer and the formability of the adhesive layer and the like are excellent. It also has excellent whitening resistance and low shrinkage.
The acrylic rubber-reinforced resin composition is excellent in the adhesion between the corona-treated layer and the anchor coat layer regardless of the constituent material of the anchor coat layer. In addition, since the thermal shrinkage rate is low, in various printing methods, even when heating is involved, deformation is difficult and good printability in the anchor coat layer is maintained. Furthermore, when the functional sheet is folded, it has excellent whitening resistance, so that a good appearance is maintained.
In the functional sheet of the present invention, the anchor coat layer includes a modified olefin composition, a polyester composition, an acrylic composition, a polyurethane composition, an isocyanate composition, a polyethyleneimine composition, and a polyamide composition. A cosmetic sheet and a pressure-sensitive adhesive sheet having a high-grade appearance when containing at least one selected from a maleic acid composition, a vinyl acetate composition, a polyvinyl butyral composition, a natural rubber composition, and a synthetic rubber composition Etc.

Hereinafter, the present invention will be described in detail.
In the present specification, “sheet” is used to include a film. Further, “adhesion” is used to mean including adhesion. Furthermore, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acrylic and methacrylic.

1. Functional sheet The functional sheet of the present invention includes a thin-walled body made of an acrylic rubber-reinforced resin composition, a corona-treated layer formed on at least one surface of the thin-walled body, and a surface of the corona-treated layer. An anchor coat layer. If it demonstrates using a schematic diagram, the functional sheet 1 of this invention will be arrange | positioned on the surface of the thin-walled body 11, the corona-treated layer 12 formed in one surface of this thin-walled body 11, and this corona-treated layer 12 Anchor coat layer 13 (see FIG. 1).

1-1. Thin-walled body The acrylic rubber-reinforced resin composition constituting the thin-walled body has a part of the (co) polymer of the vinyl-based monomer containing the aromatic vinyl compound and the vinyl cyanide compound. A composition containing an acrylic rubber-reinforced resin composed of a grafted acrylic rubbery polymer grafted on the surface of a coalescence and a (co) polymer of the above-mentioned vinyl monomer that is not grafted. . However, this acrylic rubber-reinforced resin may contain an ungrafted acrylic rubbery polymer.

The shape of the grafted acrylic rubbery polymer (however, an ungrafted acrylic rubbery polymer may be included) is not limited, and may be either a regular shape or an amorphous shape. When the shape is particulate, the number average particle diameter is 60 to 500 nm, more preferably 60 to 400 nm, still more preferably 60 to 200 nm. When the number average particle diameter is in the above range, when it is a thin body such as a film, it is excellent in shape stability and strength, and is excellent in whitening resistance when bent. The number average particle diameter of the grafted acrylic rubbery polymer is determined by immersing a thin piece prepared from the thin body according to the present invention in a solution of OsO ₄ or RuO ₄ , and then transmitting a transmission electron microscope. For example, the average particle diameter measured for 100 particles of the grafted acrylic rubber-like polymer can be used.

  The graft ratio in the acrylic rubber reinforced resin is preferably 20 to 170%, more preferably 20 to 150%, and still more preferably 30 to 150%. If the graft ratio is too low, a flow mark may be generated on the surface when a thin body such as a sheet is formed, and the mechanical strength may not be sufficient. On the other hand, if the graft ratio is too high, the viscosity of the acrylic rubber-reinforced resin composition may increase, and it may be difficult to reduce the thickness.

The graft ratio can be determined by the following formula (1).
Graft ratio (mass%) = {(S−T) / T} × 100 (1)
In the above formula, 1 g of acrylic rubber-reinforced resin is added to 20 ml of acetonitrile, shaken for 2 hours with a shaker at 25 ° C., and then centrifuged at 5 ° C. It is the mass (g) of insoluble matter obtained by centrifuging for 4 hours (rotation speed: 23,000 rpm) and separating insoluble matter and soluble matter, and T is contained in 1 gram of acrylic rubber-reinforced resin. It is the mass (g) of the acrylic rubbery polymer. The mass of the acrylic rubbery polymer can be obtained by a method of calculating from the polymerization prescription and polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  The intrinsic viscosity (measured at 30 ° C. using methyl ethyl ketone as a solvent) of the acrylic rubber-reinforced resin in acetonitrile is preferably 0.2 to 1.0 dl / g, more preferably 0.4 to 0.8 dl / g, more preferably 0.4 to 0.7 dl / g. When the above intrinsic viscosity is within this range, it is easy to form a thin body.

  The acrylic rubber reinforced resin is preferably obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber polymer having a volume average particle diameter of 60 to 500 nm. The obtained rubber-reinforced vinyl resin (A1) or a mixture of this rubber-reinforced vinyl resin (A1) and a (co) polymer (A2) of vinyl monomers, and the graft ratio is 20-170% resin.

  The acrylic rubbery polymer is a polymer made of a monomer containing a (meth) acrylic acid alkyl ester, and preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms (m1). ), And more preferably a copolymer of a monomer containing a (meth) acrylic acid alkyl ester (m1) and a polyfunctional vinyl compound (m2).

  (Meth) acrylic acid alkyl ester (m1) having 1 to 12 carbon atoms in the alkyl group includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like. These (meth) acrylic acid alkyl esters (m1) can be used singly or in combination of two or more, but the glass transition temperature of the obtained (co) polymer is 0 ° C. or less, preferably − It is selected to be 10 ° C. or lower. Of these compounds, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

The “polyfunctional vinyl compound” refers to a compound having two or more polymerizable unsaturated bonds in the molecule. Examples of the polyfunctional vinyl compound (m2) include bifunctional aromatic vinyl compounds such as divinylbenzene and divinyltoluene; 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, neopentyl glycol diacrylate, allyl acrylate, neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 3-methylpentanediol diacrylate, 3-methylpentanediol dimethacrylate, methacryl Bifunctional (meth) acrylic acid esters such as allyl acid; trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pen Trifunctional (meth) acrylic acid such as erythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate Esters; (meth) acrylic acid esters of polyhydric alcohols such as (poly) ethylene glycol dimethacrylate; diallyl malate, diallyl fumarate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, bisphenol A bis (acryloyl) Roxyethyl) ether and the like.
Of these compounds, allyl methacrylate and triallyl cyanurate are preferred. Moreover, these polyfunctional vinyl compounds (m2) can be used individually by 1 type or in combination of 2 or more types.

In order to obtain the acrylic rubbery polymer, in addition to using the (meth) acrylic acid alkyl ester (m1) and the polyfunctional vinyl compound (m2), other compounds copolymerizable with these ( m3) may be used in combination.
As said other compound (m3), a monofunctional aromatic vinyl compound, a diene compound, etc. are mentioned. These can be used alone or in combination of two or more.

Examples of the monofunctional aromatic vinyl compound include styrene, p-methylstyrene, α-methylstyrene, and the like. Of these, styrene is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
Examples of the diene compound include butadiene and isoprene. These can be used alone or in combination of two or more.

  The amount of each monomer used to make the acrylic rubbery polymer is (meth) acrylic acid alkyl ester (m1), polyfunctional vinyl compound (m2) when the total amount is 100% by mass. And in the order of the other compound (m3), respectively, preferably 80 to 99.99% by mass, 0.01 to 5% by mass, and 0 to 19.99% by mass, and more preferably 90 to 99.5%. Mass%, 0.1-2.5 mass% and 0-9.9 mass%. By making the usage-amount of each monomer into the said range, the effect made into the objective of this invention can be made into a high level.

  The acrylic rubbery polymer can be obtained by emulsion polymerization by a conventional method while stirring a mixture containing the monomer, an emulsifier, a polymerization initiator, and water. In addition, you may mix | blend a chain transfer agent (molecular weight regulator), electrolyte, etc. with the said mixture.

As emulsifiers, alkyl sulfonates such as alkane sulfonate, alkylbenzene sulfonate, and alkyl naphthalene sulfonate; gum rosin, wood rosin, tall oil rosin, disproportionated rosin obtained by disproportionating these, and purified rosin Rosinates such as alkali metal salts (sodium salt or potassium salt) of rosin acid (usually mainly abietic acid) such as sulfates of higher alcohols, higher aliphatic carboxylates, phosphates, etc. Anionic surfactants; nonionic surfactants and the like.
The usage-amount of the said emulsifier is 0.1-10 mass parts normally, when the whole quantity of the said monomer is 100 mass parts, Preferably it is 0.5-5 mass parts.

  As polymerization initiators, cumene hydroperoxide, diisopropylbenzene hydroperoxide, benzoyl peroxide, lauroyl peroxide, potassium persulfate, azobisisobutyronitrile, tert-butylperoxylaurate, tert-butylperoxymono And carbonate. These can be used alone or in combination of two or more. The polymerization initiator can be added to the reaction system all at once or continuously. Moreover, the usage-amount of the said polymerization initiator is 0.01-3 mass parts normally, when the whole quantity of the said monomer is 100 mass parts, Preferably it is 0.05-2 mass parts.

  Examples of chain transfer agents include mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol and the like. It is done. These can be used alone or in combination of two or more. Moreover, the usage-amount of the said chain transfer agent is 0-5 mass parts normally, when the whole quantity of the said monomer is 100 mass parts, Preferably it is 0-3 mass parts.

The volume average particle diameter of the acrylic rubbery polymer is preferably 60 to 500 nm, more preferably 60 to 400 nm, and still more preferably 60 to 200 nm. When the volume average particle diameter is in the above range, even when a thin body having a small film thickness is obtained, the shape stability and strength are excellent, and the whitening resistance when bent is improved. In addition, the volume average particle diameter of the acrylic rubbery polymer can be measured by a dynamic light scattering method.
The volume average particle diameter of the acrylic rubbery polymer is determined by the type and amount of emulsifier, the type and amount of polymerization initiator used in the production of the acrylic rubbery polymer, the polymerization rate (polymerization temperature, polymerization start). It can be adjusted by appropriately selecting the method of adding the agent and the like, the stirring speed and the like.

The gel content of the acrylic rubbery polymer is preferably 20 to 99%, more preferably 30 to 98%, and still more preferably 40 to 98%. When the gel content is in the above range, the balance between physical properties of calender molding process and impact resistance is excellent.
In addition, the said gel content rate can be calculated | required with the following method. First, 1 gram of the acrylic rubbery polymer is put into 20 ml of acetonitrile, and stirred at 1,000 rpm for 2 hours under a temperature condition of 25 ° C. using a stirrer. Thereafter, the mixture is centrifuged for 1 hour with a centrifuge (rotation speed: 22,000 rpm), the insoluble matter obtained by separating the insoluble matter and the soluble matter is weighed (mass is defined as W ₁ gram), and the following. Calculate by the formula.
Gel content (%) = [W ₁ (g) / 1 (g)] × 100
The gel content is adjusted by appropriately selecting the type and amount of the polyfunctional vinyl compound, the type and amount of the molecular weight regulator, the polymerization time, the polymerization temperature, the polymerization conversion rate, etc. during the production of the rubbery polymer. The
The acrylic rubbery polymer can be used alone or in combination of two or more.

On the other hand, the vinyl monomer includes an aromatic vinyl compound and a vinyl cyanide compound.
Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, vinyl xylene, ethyl styrene, dimethyl styrene, methyl-α-methyl styrene, p-tert-butyl styrene. Vinyl naphthalene, methoxystyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, and the like. Of these, styrene and α-methylstyrene are preferred. Moreover, these compounds can be used individually by 1 type or in combination of 2 or more types.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-chloro (meth) acrylonitrile and the like. Of these, acrylonitrile is preferred. Moreover, these compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition to the above aromatic vinyl compound and vinyl cyanide compound, the vinyl monomer may be other compounds copolymerizable with these. Other compounds include (meth) acrylic acid ester, maleimide compound, functional group-containing unsaturated compound (for example, unsaturated acid, epoxy group-containing unsaturated compound, hydroxyl group-containing unsaturated compound, oxazoline group-containing unsaturated compound, Acid anhydride group-containing unsaturated compounds, etc.). These can be used alone or in combination of two or more.

(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate and the like. These can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.
Examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like. These can be used alone or in combination of two or more.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used alone or in combination of two or more. In order to introduce a maleimide monomer unit into the copolymer resin, maleic anhydride may be (co) polymerized and post-imidized.

  Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. These can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2. -Methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxystyrene and the like. These can be used alone or in combination of two or more.

Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline. These can be used alone or in combination of two or more.
Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.

As the vinyl monomer, the type and amount used are selected according to the purpose, application, etc., but when mainly an aromatic vinyl compound and a vinyl cyanide compound are used, the total amount of these compounds is The amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the vinyl monomer. In addition, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound is preferably 60 to 85% by mass and 15 to 40% by mass, and more preferably 70 to 70% by mass when the total of these is 100% by mass. 80 mass% and 20-30 mass%.
In order to obtain a transparent or transparent acrylic rubber-reinforced resin composition, it is preferable to use a (meth) acrylic ester as the vinyl monomer. The amount of the (meth) acrylic acid ester used is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total amount of the vinyl monomer. The balance is an aromatic vinyl compound and a vinyl cyanide compound, and the usage ratio thereof is the same as described above.

  The production method of the rubber-reinforced vinyl resin (A1) is not particularly limited, and a known polymerization method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like can be applied. Of these, emulsion polymerization is preferred. The combination of the amounts of the acrylic rubbery polymer and the vinyl monomer is preferably 5 to 70% by mass and 30 to 95% by mass, respectively, when the total amount is 100 parts by mass. More preferably, they are 10-65 mass% and 35-90 mass%.

When the rubber-reinforced vinyl resin (A1) is produced by emulsion polymerization, a polymerization initiator, an emulsifier, a chain transfer agent (molecular weight regulator), an electrolyte, water, and the like are used. In addition, although an emulsifier and a chain transfer agent may not be used depending on the situation, they are usually used.
As the polymerization initiator, the compounds exemplified in the description of the method for producing the acrylic rubbery polymer can be used. The polymerization initiator can be added to the reaction system all at once or continuously. Moreover, the usage-amount of the said polymerization initiator is 0.1-5 mass parts normally, when the whole quantity of the said vinylic monomer is 100 mass parts, Preferably it is 0.5-2 mass parts.
The compounds exemplified above can also be used for the emulsifier and the chain transfer agent. In addition, the usage-amount of the said emulsifier is 0.1-5 mass parts normally, when the whole quantity of the said vinylic monomer is 100 mass parts, Preferably it is 0.1-3 mass parts. Moreover, the usage-amount of the said chain transfer agent is 0.01-5 mass parts normally, when the whole quantity of the said vinylic monomer is 100 mass parts, Preferably it is 0.05-3 mass parts.

When the rubber-reinforced vinyl resin (A1) is produced by emulsion polymerization, the acrylic rubbery polymer and the vinyl monomer are used in the presence of the entire amount of the acrylic rubbery polymer. The polymer may be polymerized by batch addition or polymerization may be performed while being divided or continuously added. Further, in the presence of a part of the acrylic rubber polymer, polymerization may be carried out by adding vinyl monomers all at once and adding the remainder of the acrylic rubber polymer during the polymerization. The polymerization may be carried out by dividing or continuously adding a vinyl monomer and adding the remainder of the acrylic rubber polymer during the polymerization.
In addition, the polymerization temperature in the case of emulsion polymerization is 30-95 degreeC normally, Preferably it is 40-90 degreeC.

  To extract the rubber-reinforced vinyl resin (A1) from the latex obtained by emulsion polymerization, usually an inorganic salt such as calcium chloride, magnesium sulfate or magnesium chloride; an acid such as sulfuric acid, hydrochloric acid, acetic acid, citric acid or malic acid It is performed by adding a coagulant such as. Thereafter, the solidified rubber-reinforced vinyl resin (A1) is obtained as a powder by washing with water and drying.

  Moreover, when manufacturing the said rubber | gum reinforcement | strengthening vinyl-type resin (A1) by solution polymerization, block polymerization, or suspension polymerization, it can carry out by a conventional method. In the case of solution polymerization, usually a vinyl monomer is dissolved in an aromatic hydrocarbon such as toluene or ethylbenzene; ketones such as methyl ethyl ketone; an inert polymerization solvent such as acetonitrile, dimethylformamide, N-methylpyrrolidone, or the like. Polymerization may be performed in the presence of an initiator, or thermal polymerization may be performed in the absence of a polymerization initiator.

  The rubber-reinforced vinyl resin (A1) obtained by the above method is usually a grafted acrylic in which a part of the vinyl monomer (co) polymer is grafted on the surface of the acrylic rubbery polymer. And a non-grafted component which is a (co) polymer of a vinyl monomer. The residual amount of the vinyl monomer remaining in the acrylic rubber reinforced resin is usually 10,000 ppm or less, preferably 5,000 ppm or less.

  The acrylic rubber reinforced resin may be composed of only one kind of rubber reinforced vinyl resin (A1), or may be composed of two or more kinds.

Further, as described above, the acrylic rubber reinforced resin may be only the rubber reinforced vinyl resin (A1), or may be obtained by polymerization of the rubber reinforced vinyl resin (A1) and a vinyl monomer. A mixture with the (co) polymer (A2) may also be used. The vinyl monomer is not particularly limited as long as it has a polymerizable unsaturated bond, and examples thereof include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimide compounds, functional groups. Group-containing unsaturated compounds (for example, unsaturated acids, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds) and the like. As these monomers, the compounds exemplified in the description of the acrylic rubber-reinforced resin can be used.
The vinyl monomer may be the same type of compound as the vinyl monomer used to form the acrylic rubber-reinforced resin, or may be a different compound. Moreover, when using two or more compounds of the same kind, the use ratio may be the same or different.
In addition, in order to obtain a transparent or transparent acrylic rubber-reinforced resin composition, a homopolymer of (meth) acrylic acid ester, or (meth) acrylic acid ester and other vinyl type It is preferable to use a copolymer with a monomer as the (co) polymer (A2).

The (co) polymer (A2) can be obtained by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like.
The intrinsic viscosity (measured at 30 ° C. using methyl ethyl ketone as a solvent) of the (co) polymer (A2) is preferably 0.2 to 1.2 dl / g, more preferably 0.25 to 0.9 dl / g.

  When the acrylic rubber reinforced resin is a mixture of the rubber reinforced vinyl resin (A1) and the (co) polymer (A2), the blending ratio of the (co) polymer (A2) is acrylic rubber reinforced. The content of the acrylic rubbery polymer (used for forming the rubber-reinforced vinyl resin (A1)) in the resin is adjusted to be within a predetermined range as described later.

The graft ratio in the acrylic rubber-reinforced resin is as follows: the type and amount of chain transfer agent used during the production of the rubber-reinforced vinyl resin (A1), the type and amount of polymerization initiator, and the monomer component during polymerization. It can be adjusted by appropriately selecting the addition method, addition time, and the like.
In addition, regarding the intrinsic viscosity in the acrylic rubber-reinforced resin, the type and amount of chain transfer agent used in the production of the rubber-reinforced vinyl resin (A1) and (co) polymer (A2), the type of polymerization initiator In addition, it can be adjusted by appropriately selecting the amount used, polymerization temperature, and the like.

  The amount of bound vinyl cyanide compound (hereinafter also referred to as “bound VC amount”) of the acrylic rubber-reinforced resin in which acetonitrile is soluble is preferably 3 to 40% by mass, more preferably 10 to 30% by mass. It is. When this amount of bonded VC is in the above range, the acrylic rubber-reinforced resin composition is excellent in molding processability, and the resulting thin-walled body is also excellent in appearance and chemical resistance. The amount of bound VC can be adjusted by the ratio of the vinyl cyanide compound added at the time of polymerization, and the value is determined by using the acetonitrile soluble matter obtained in the pretreatment when determining the graft ratio as a measurement sample. It can obtain by the liquid chromatography which applied the conditions described in the Example mentioned later.

More preferably, the acrylic rubber-reinforced resin is a resin containing a unit made of an aromatic vinyl compound and a unit made of a vinyl cyanide compound, and has a graft ratio of 20 to 170%. The number average particle size of the polymer is 60 to 200 nm, the intrinsic viscosity of acetonitrile soluble matter is 0.4 to 0.8 dl / g, and the amount of bound vinyl cyanide compound of acetonitrile soluble matter is 3 to 40. A resin having a mass deviation of 5% or less and a standard deviation of the distribution of the bound vinyl cyanide compound amount measured by liquid chromatography being 5 or less.
The graft ratio is more preferably 30 to 160%, still more preferably 80 to 160%.
The number average particle diameter is more preferably 60 to 180 nm, still more preferably 70 to 150 nm.
The intrinsic viscosity is more preferably 0.5 to 0.8 dl / g, still more preferably 0.5 to 0.7 dl / g.
The amount of the bound vinyl cyanide compound (bound VC amount) is more preferably 10 to 40% by mass, and still more preferably 20 to 30% by mass. When the amount of the combined VC is in the above range, the appearance of the thin film body is excellent. The standard deviation of the distribution of the bound VC amount can be obtained by liquid chromatography applying the conditions described in the examples described later.
The standard deviation of the amount of bound vinyl cyanide compound (bound VC amount) is more preferably 4 or less. If this standard deviation is too large, the flow mark may become prominent on the surface of the thin-walled body. Incidentally, the standard deviation of the distribution of the bound VC amount in the production steps of the rubber-reinforced vinyl resin (A1) and the (co) polymer (A2) constituting the resin is the same as the monomer component in the reaction system. The ratio of the vinyl cyanide compound is adjusted to a value obtained from the copolymerization reactivity ratio.

  The acrylic rubber reinforced resin composition according to the present invention may be composed only of the above acrylic rubber reinforced resin, or may contain this acrylic rubber reinforced resin and other components. . Examples of other components include polymers and additives.

  Examples of the polymer include ABS resin, AES resin, polycarbonate resin, thermoplastic polyester resin (PET, PBT, etc.), polyamide resin, polyamide elastomer, and polyester elastomer. These polymers can be used alone or in combination of two or more.

  Examples of the additives include ultraviolet absorbers, weathering agents, fillers, antioxidants, anti-aging agents, antistatic agents, flame retardants, antifogging agents, lubricants, antibacterial agents, tackifiers, plasticizers, colorants, and the like. Is mentioned.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
Content of the said ultraviolet absorber is 0.05-5 mass parts normally with respect to 100 mass parts of all the polymers containing the said acrylic rubber reinforced resin.

Examples of the weathering agent include organic phosphorus compounds, organic sulfur compounds, and organic compounds containing a hydroxyl group. These can be used alone or in combination of two or more.
Content of the said weathering agent is 0.1-5 mass parts normally with respect to 100 mass parts of all the polymers containing the said acrylic rubber reinforced resin.

Examples of the filler include talc, titanium oxide, clay, calcium carbonate and the like. These can be used alone or in combination of two or more.
Content of the said filler is 0.05-20 mass parts normally with respect to 100 mass parts of all the polymers containing the said acrylic rubber reinforced resin.

  The content of the acrylic rubber-like polymer in the acrylic rubber-reinforced resin composition according to the present invention is preferably 2 to 45% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 35% by mass. is there. When the content of the acrylic rubbery polymer is within this range, the thin-walled body made of the acrylic rubber-reinforced resin composition has sufficient strength.

The thin-walled body according to the present invention is made of the above acrylic rubber-reinforced resin composition, and can be produced by calendar molding, inflation molding, T-die extrusion molding, or the like. The thickness is usually 30 to 500 μm, preferably 40 to 400 μm, more preferably 50 to 400 μm.
Moreover, the surface of the said thin body may be a smooth surface, and may have a regular pattern or an irregular pattern by hairline processing, embossing, etc.

  The thin-walled body has a heat shrinkage rate (in accordance with JIS K7133, temperature rough adjustment at 80 ° C. for 30 minutes), preferably 1% or less in the vertical direction and 1% or less in the horizontal direction, and more preferably in the vertical direction. It is 0.8% or less in the direction and 0.8% or less in the lateral direction. Therefore, when the anchor coat layer is laminated and then left at a high temperature, or in various printing methods, the generation of wrinkles or deformation is suppressed when heating is involved, and good printability and appearance can be maintained. it can. This heat shrinkage rate is the same when the corona treatment layer is formed.

1-2. Corona treatment layer In the functional sheet of the present invention, a corona treatment layer is formed on the surface (one side or both sides) of the thin body. This corona treatment layer was obtained using a known corona treatment device (the detailed method is the same as the “corona treatment step” in the method for producing a functional sheet described later). The surface of this corona-treated layer has increased functional groups such as> C = O and -COOH as compared with the untreated surface, and the wetting index according to JIS K6768 is usually 40 mN / m or more, preferably Is 43 mN / m or more, more preferably 45 mN / m or more. If the wetting index is too small, the anchor coat layer may be peeled off.

  The surface of the corona treatment layer may be subjected to surface processing such as hairline processing or embossing.

1-3. Anchor coat layer In the functional sheet of the present invention, an anchor coat layer is disposed on the surface of the corona-treated layer (see FIG. 1). This anchor coat layer is usually a film mainly composed of a polymer, and for purposes such as strength improvement and decoration, fillers, metallic glossy particles, dispersants, antifoaming agents, viscosity, as necessary. Adjusting agent, film-forming aid, pH adjusting agent, antiseptic, antifungal agent, ultraviolet absorber, weathering agent, antioxidant, anti-aging agent, antistatic agent, flame retardant, antifogging agent, lubricant, antibacterial agent, Includes tackifiers, plasticizers, colorants and the like.
The anchor coat layer is preferably a modified olefin composition, a polyester composition, an acrylic composition, a polyurethane composition, an isocyanate composition, a polyethyleneimine composition, a polyamide composition, or a maleic acid composition. A layer composed of at least one composition selected from a rubber composition, a vinyl acetate composition, a polyvinyl butyral composition, a natural rubber composition, and a synthetic rubber composition. Of these, acrylic compositions, polyurethane compositions and polyethyleneimine compositions are preferred. When these compositions are used, the adhesiveness with the corona-treated layer is excellent, and the printability on the surface of the anchor coat layer is also excellent. Further, another layer can be easily laminated on the surface of the anchor coat layer.

The surface of the anchor coat layer may be a glossy surface or a non-glossy surface. In the case of the latter non-glossy surface, it may have a matte property. When it has a matte property, it is preferable that the said composition contains the microparticles | fine-particles which consist of at least 1 sort (s) chosen from the polymer and the inorganic compound.
Examples of the polymer include polystyrene polymers; acrylic polymers such as polymethyl methacrylate and methyl methacrylate / ethylene glycol dimethacrylate copolymer; polyamide resins; polytetrafluoroethylene and the like. These may be included alone or in combination.
Examples of inorganic compounds include silica, titania, calcium carbonate, alumina, talc, clay, barium sulfate and the like. These may be included alone or in combination.
The average particle diameter of the fine particles is preferably 0.1 to 6 μm, more preferably 0.2 to 5 μm. If the average particle size is too small, the desired matte surface may not be obtained. On the other hand, when the average particle size is too large, the appearance may be deteriorated.

The anchor coat layer has a thickness of preferably 0.01 to 10 μm, more preferably 0.02 to 8 μm, and still more preferably 0.05 to 7 μm. If it is this range, it will be excellent in the printability in the surface of an anchor coat layer, and the formability of an adhesion layer.
In addition to the embodiment shown in FIG. 1, the functional sheet of the present invention includes a thin body 11, corona treatment layers 12a and 12b formed on both sides thereof, and the surface of the corona treatment layer 12a as shown in FIG. It can also be set as functional sheet | seat 1 'provided with the anchor-coat layer 13 arrange | positioned by.

The thickness of the functional sheet of the present invention is preferably 30 to 500 μm, more preferably 40 to 400 μm, and still more preferably 50 to 400 μm.
In the present invention, the thermal contraction rate of the functional sheet comprising the thin-walled body, the corona-treated layer, and the anchor coat layer (according to JIS K7133, at 30 ° C. for 30 minutes) is preferably longitudinally adjusted. 1% or less, 1% or less in the horizontal direction, more preferably 0.8% or less in the vertical direction, and 0.8% or less in the horizontal direction. Therefore, deformation of the printed image on the surface of the anchor coat layer can be suppressed, and a stable shape can be maintained even when another layer is laminated on the surface of the anchor coat layer.

2. Method for producing functional sheet The functional sheet of the present invention comprises a corona treatment step for corona treatment on at least one surface of a thin-walled body made of an acrylic rubber-reinforced resin composition to form a corona treatment layer, and the corona treatment The surface of the layer is water-based and modified olefin-based composition, polyester-based composition, acrylic-based composition, polyurethane-based composition, isocyanate-based composition, polyethyleneimine-based composition, polyamide-based composition, maleic acid A coating step of applying at least one anchor coating composition selected from a system composition, a vinyl acetate composition, a polyvinyl butyral composition, a natural rubber composition, and a synthetic rubber composition (Hereinafter referred to as “the present production method”).

In the corona treatment process according to this production method, a grounded dielectric coated roll (generally, the roll core is made of iron or aluminum, and the dielectric is made of silicon, high pylon, EPT, or ceramic). ) And a knife-like electrode disposed at intervals of several mm to generate a corona discharge, and an acrylic rubber-reinforced resin composition between the electrode and the roll during the discharge. And a thin body having a thickness of 30 to 500 μm is passed through.
Corona treatment may be performed only on one side of the thin-walled body or on both sides.

The corona treatment is usually performed in an air atmosphere, but may be performed in an inert gas atmosphere such as nitrogen gas. In the treatment conditions, the discharge amount is usually 40 W · min / m ² or more, preferably 43 to 80 W · min / m ² , more preferably 48 to 80 W · min / m ² .
The above discharge amount is obtained by the following equation, where the discharge electrode length is L (m), the thin-body speed is V (m / min), and the discharge power is P (W).

When the corona treatment is performed in an air atmosphere, when a high voltage is applied, corona discharge is generated between the electrode and the thin-walled body, and ozone O ₃ is generated. The ozone O ₃ receives discharge energy and generates oxygen radicals (free radicals) O. Further, this oxygen radical O. oxidizes —CH ₃ , —CH ₂ — and the like contained in the acrylic rubber-reinforced resin constituting the thin-walled body to form carbonyl C═O.

In the coating step according to this production method, a water-based anchor coat composition is applied to the surface of the corona treatment layer formed by the corona treatment step.
This anchor coat composition is high in water alone or in a mixed medium containing water as a main component and at least one organic compound selected from alcohol, ester, ketone and ether as necessary. Modified olefin-based composition, polyester-based composition, acrylic-based composition, polyurethane-based composition, isocyanate-based composition, polyethyleneimine-based composition, polyamide-based composition in which molecules or polymer precursors are dissolved or dispersed A maleic acid composition, a vinyl acetate composition, a polyvinyl butyral composition, a natural rubber composition, a synthetic rubber composition, and the like are preferable. This composition may be either a crosslinked type or a non-crosslinked type.

The above-mentioned anchor coat composition is filled with fillers, metallic glossy particles, dispersants, antifoaming agents, viscosity modifiers, film-forming aids, pH adjusters, antiseptics, antifungal agents, and UV absorbers as necessary. Agents, weathering agents, antioxidants, anti-aging agents, antistatic agents, flame retardants, antifogging agents, lubricants, antibacterial agents, tackifiers, plasticizers, colorants and the like.
The solid content concentration of the anchor coat composition is usually 0.2 to 50% by mass, preferably 0.5 to 40% by mass.

The method for applying the anchor coating composition is selected from a gravure coating method, a reverse coating method, a knife coating method, a kiss coating method, and the like depending on the type and viscosity of the composition.
After the application step, the anchor coat layer can be obtained by drying the coating film, usually by heating.

  After forming the anchor coat layer as described above, the surface may be subjected to a smoothing process, a glossing process, or the like by a calender device or the like, if necessary. Further, a primer layer or the like may be further laminated on the surface of the anchor coat layer.

  In addition, in order to provide the surface of the anchor coat layer with matte properties, the anchor coat composition preferably contains fine particles composed of at least one selected from a polymer and an inorganic compound. The type and average particle size are as described above.

3. Functional sheet having matte layer Another functional sheet of the present invention is a laminated functional sheet 2 as shown in FIG. 3, for example, and includes the thin body 11 and the surface of the thin body 11. The corona-treated layer 12 is formed on the surface of the corona-treated layer 12, and the matte layer 14 is disposed on the surface of the anchor-coated layer 13. The anchor coat layer 13 does not usually contain the fine particles described above, but may contain the fine particles.

The matting layer is usually a layer containing a matting material and a binder.
The matte material can be the same as the fine particles with respect to the type and average particle size.
Examples of the binder include acrylic resins, polyester resins, alkyd resins, silicone resins, cellulose derivatives, urethane resins, vinyl chloride resins, fluorine resins, vinyl acetate resins, and the like. It is done.

The matting layer may be a dispersant, an antifoaming agent, a viscosity adjusting agent, a film forming aid, a pH adjusting agent, an antiseptic, an antifungal agent, an ultraviolet absorber, a weathering agent, an antioxidant, or an aging as necessary. It may contain additives such as an inhibitor, an antistatic agent, a flame retardant, an antifogging agent, a lubricant, an antibacterial agent, a tackifier, a plasticizer, and a colorant.
The thickness of the matte layer is preferably 0.5 to 10 μm, more preferably 0.8 to 8 μm, and still more preferably 1 to 8 μm. If it is this range, sufficient matting effect will be acquired.

  The matte layer is applied to the surface of the anchor coat layer with a matting agent composition that is water-based and includes a polymer for forming a coating film that forms the binder and fine particles. It can be formed by drying.

  The content of the fine particles in the matting agent composition is usually 10 to 150 parts by mass, preferably 15 to 130 parts by mass, when the coating film forming polymer (solid content) is 100 parts by mass.

The medium of the matting agent composition is an aqueous medium mainly composed of water, and the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.
The matting agent composition is applied by spray coating, brush coating, roller coating, trowel coating, flow coater coating, roll coater coating, knife coating, gravure coating, depending on the type and viscosity of the composition. , Selected from electrostatic coating and the like.
After the coating step, if necessary, the coating film can be dried by heating or the like to obtain a matte layer.

When the other functional sheet of the present invention has the structure shown in FIG. 3, an adhesive layer or the like may be further disposed on the lower side of the thin body 11. In that case, a corona treatment layer may be formed in advance on the lower side of the thin-walled body 11.
When laminating the pressure-sensitive adhesive layer, a composition for forming a pressure-sensitive adhesive layer containing a polymer, a tackifier, a solid plasticizer, or the like on the back surface of the thin-walled body 11 or the surface when a corona-treated layer is formed. (Adhesive composition) may be applied directly or, if necessary, a primer layer or the like may be formed, and then an adhesive layer forming composition may be applied. By forming this primer layer, the coating property of the composition for forming an adhesive layer, the smoothness of the formed adhesive layer, and the like can be improved. In any case, after the application of the pressure-sensitive adhesive composition, it is appropriately dried and a release paper or the like is provided. When the pressure-sensitive adhesive layer is a heat-sensitive pressure-sensitive adhesive layer, the release paper need not be provided.

  In the functional sheet of the present invention, offset printing, gravure printing, screen printing, ink jet printing and the like can be performed on the surface of the anchor coat layer or the matte layer, and the adhesion (fixability) of the printed image. Excellent.

  Hereinafter, the present invention will be described more specifically with reference to examples. In Examples and Comparative Examples, parts and% are based on mass unless otherwise specified.

1. Acrylic rubber reinforced resin and polybutadiene rubber reinforced resin An acrylic rubber reinforced resin using a rubber reinforced vinyl resin obtained by the following Production Examples 1, 2, 3 and 4 and an acrylonitrile / styrene copolymer described later. A polybutadiene rubber reinforced resin was prepared.
(1) Rubber reinforced vinyl resin (A1)
Production Example 1
Using the raw material components shown in Table 1, a rubber-reinforced vinyl resin (A1-1) was produced in the following manner.
Solid content containing acrylic rubbery polymer having a volume average particle diameter of 100 nm and a gel content of 90%, obtained by emulsion polymerization of 99 parts of n-butyl acrylate and 1 part of allyl methacrylate in a reactor. 50 parts of latex with a concentration of 40% (in terms of solid content) was added, and further diluted with 1 part of sodium dodecylbenzenesulfonate and 150 parts of ion-exchanged water. Thereafter, the inside of the reactor was replaced with nitrogen gas, and 0.02 part of disodium ethylenediaminetetraacetate, 0.005 part of ferrous sulfate and 0.3 part of sodium formaldehydesulfoxylate were added, and the temperature was raised to 60 ° C. with stirring. Warm up.
On the other hand, 1.0 part of terpinolene and 0.2 part of cumene hydroperoxide are dissolved in 50 parts of a mixture of 37.5 parts of styrene and 12.5 parts of acrylonitrile in a container, and then the inside of the container is replaced with nitrogen gas. A monomer composition was obtained.
Next, polymerization was performed at 70 ° C. while adding the monomer composition to the reactor at a constant flow rate over 5 hours to obtain a latex. Magnesium sulfate was added to this latex to coagulate the resin component. Then, rubber reinforced vinyl resin (A1-1) was obtained by washing with water and further drying.

Production Example 2
A rubber-reinforced vinyl-based resin (A1) was prepared in the same manner as in Production Example 1 except that an acrylic rubbery polymer having a volume average particle diameter of 40 nm was used and the amounts of acrylonitrile and styrene used were those shown in Table 1. -2) was obtained.

Production Example 3
A rubber-reinforced vinyl resin (A1-3) was obtained in the same manner as in Production Example 1 except that the amounts of acrylonitrile and styrene used were those shown in Table 1.

Production Example 4
A rubber-reinforced vinyl resin (A1-4) was obtained in the same manner as in Production Example 3 except that a polybutadiene rubber polymer having a volume average particle diameter of 110 nm was used.

(2) Acrylonitrile / styrene copolymer (A2)
An acrylonitrile / styrene copolymer having a bound VC amount (bound acrylonitrile amount) of 24.0% and an intrinsic viscosity (measured at 30 ° C. using methyl ethyl ketone as a solvent) was 0.45 dl / g.

(3) Acrylic rubber reinforced resin and polybutadiene rubber reinforced resin The acrylic rubber reinforced resins used in the following experiments are three types (B-1), (B-2) and (B-3). Resins (B-1) and (B-2) were prepared by feeding the rubber-reinforced vinyl resin (A1) and the acrylonitrile / styrene copolymer (A2) into a Henschel mixer at the ratio shown in Table 2. Thereafter, the mixture was supplied to a twin screw extruder and melt-kneaded at a temperature of 200 to 240 ° C. to obtain pellets. Resins (B-3) and (B-4) were supplied as they were to a twin-screw extruder and melt-kneaded at a temperature of 200 to 240 ° C. to obtain pellets. For these resins (B-1) to (B-4), the graft ratio, the number average particle diameter of the grafted acrylic rubber polymer or grafted polybutadiene rubber polymer, the intrinsic viscosity of the acetonitrile-soluble component and the binding The amount of VC (bound acrylonitrile amount) and the standard deviation of the bound acrylonitrile amount were measured and listed in Table 2. The amount of bound acrylonitrile in the acetonitrile-soluble component was measured by high performance liquid chromatography by the following method.

<Measurement method of bound acrylonitrile amount (bound VC amount) and standard deviation of its distribution>
20 mg of acetonitrile-soluble component of the acrylic rubber-reinforced resin was dissolved in 5 ml of a mixed solvent of acetonitrile / 1,2-dichloroethane having a volume ratio of 6/4 and left for 24 hours. Then, it filtered with a 0.5 micrometer filter and prepared the sample for liquid chromatography. This sample was analyzed under the following conditions, and using the obtained elution curve, the amount of bound acrylonitrile and the standard deviation of its distribution were obtained from the elution amount% and the acrylonitrile amount. At this time, an acrylonitrile / styrene copolymer whose amount of bound acrylonitrile was determined by CHN elemental analysis was used as a standard sample.
Column TSKgel Silica-60 15cm (manufactured by Tosoh Corporation)
Eluent A liquid n-heptane / 1,2-dichloroethane (volume ratio 7/3)
Liquid B Acetonitrile / 1,2-dichloroethane (volume ratio 6/4)
Gradient condition B liquid: 25% → 100% (19 minutes, linear gradient), 100% (10 minutes, hold), 100% → 25% (5 minutes, linear gradient), 25% (5 minutes, hold)
Flow rate 1 ml / min Column temperature 30 ° C
Injection volume 20 μl
Detector UV (wavelength 260nm)

2. Production and evaluation of functional sheets (I)
Example 1
The acrylic rubber reinforced resins (B-1), (B-2) and (B-3) prepared above were used as the acrylic rubber reinforced resin composition, respectively.
First, pellets made of the acrylic rubber-reinforced resin were melted at 180 to 190 ° C. and further kneaded using a hot roll. Thereafter, the kneaded product is rolled using a calender device having a calender roll adjusted to a temperature of 190 ° C., and is a long film (thin body) having a width of 1,000 mm and a thickness of 150 μm (F1) to (F3). Was made. When this film was allowed to stand in a dryer at a temperature of 80 ° C. for 30 minutes and the heat shrinkage rate was measured according to JIS K7133, the values shown in Table 3 were obtained.
After that, at a predetermined position of a table type processing apparatus (high frequency power supply type “AGI-021S”, manufactured by Kasuga Denki Co., Ltd.) having a quartz electrode (discharge electrode length 0.28 m), a size of A4 size (297 mm long and 210 mm wide). The films (F1) to (F3) cut into pieces were set so that the distance between the electrode and the film was 1.5 mm, and under the conditions shown in Table 3, the film speed was changed to perform corona treatment. The wettability on the corona-treated surface of each film table after corona treatment was determined, and the wettability index was also shown in Table 3.
The method for determining the wetting index is as follows. Wet tension test mixture (ethylene glycol monoethyl ether amide, manufactured by Wako Pure Chemical Industries, Ltd.) was subjected to corona treatment of each film with a cotton swab (trade name “HUBY-340 CA-002 cotton applicator”, manufactured by Sanyo Co., Ltd.). It applied to the surface and the wettability was determined according to JIS K6768.

Next, on the corona-treated surface of each film, an aqueous polyurethane resin dispersion (trade name “Takelac XW-725-B186C”, manufactured by Mitsui Takeda Chemical Co., Ltd., solid content concentration 50%), ion-exchanged water, and isopropyl alcohol are added. An anchor coat composition [ac1] prepared by mixing at a pure ratio of 1/1/12/12 was applied with a bar coater # 5 and dried in a dryer at 80 ° C. for 3 minutes to form an anchor coat layer. As a result, functional sheets (S1) to (S5) were obtained.
The obtained functional sheets (S1) to (S5) were evaluated with respect to the adhesion of the anchor coat layer, the whitening resistance, and the thermal shrinkage of the functional sheet. The results are shown in Table 3. Each evaluation method is as follows.
(I) Adhesiveness Adhesive tape (manufactured by Nitto Co., Ltd.) having a width of 18 mm and a length of about 75 mm was attached to the surface of the anchor coat layer, and it was adhered with finger pressure and then peeled off at once. It was visually determined whether or not the anchor coat layer remained. The adhesive tape was attached and peeled according to JIS K5600-5-6. As a criterion, “◯” indicates that the adhesion is good and that there is no problem in practical use, “△” indicates that the adhesion is slightly inferior, and “×” indicates that the anchor coat layer has been peeled off, Each means.
(Ii) Whitening resistance The obtained functional sheet was bent 180 ° at a temperature of 23 ° C., and the bent portion was observed and evaluated according to the following criteria.
○: Almost no whitening and good.
Δ: Slightly inferior to ○.
X: Whitening was confirmed and it was bad.

Comparative Example 1
Using the film (F1) in Table 3, the corona treatment was omitted, and a functional sheet (S6) was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 2
A functional sheet (S7) was produced in the same manner as in Example 1 (1) in Table 3 except that the polybutadiene rubber reinforced resin (B-4) prepared above was used, and various evaluations were performed. The results are shown in Table 3.

3. Production and evaluation of functional sheets (II)
Example 2
The following three types of anchor coat compositions [ac2], [ac3] and [ac4] were applied to the corona-treated surfaces of the three corona-treated films of Example 1 (1) in Table 3 using a bar coater # 5. The functional sheets (S8) to (S19) were obtained by drying for 3 minutes in a dryer at 80 ° C. to form an anchor coat layer.

[Ac2]: A polyurethane resin aqueous dispersion (trade name “Takelac XW-725-B186C”, manufactured by Mitsui Takeda Chemical Co., Ltd., solid content concentration 50%), ion-exchanged water, and isopropyl alcohol are used at a pure fraction ratio of 100 / Prepared by mixing 4115/4115.
[Ac3]; Acrylic copolymer emulsion (trade name “MK-100IP”, manufactured by Shin-Nakamura Chemical Co., Ltd., solid content concentration 40%) and isopropyl alcohol are mixed at a pure content ratio of 100 / 6566.7. Prepared.
[Ac4]; Polyethyleneimine-based primer (trade name “AD-372MW”, manufactured by Toyo Morton, solid content concentration 7%), ion-exchanged water, and isopropyl alcohol, pure ratio 100 / 531.4 / 531 Prepared by mixing in .4.

尚、展色印刷の条件は、ＲＩテスター４分割ロールにインキを０．０７５ｃｃ盛、空冷メタルハライドランプ１灯を、出力１１２Ｗ／ｃｍ及び速度３０ｍ／分で照射し、インキを固化させた。
（ｉｉｉ）密着性（印刷定着性）
印刷面に、幅１８ｍｍ及び長さ約７５ｍｍの粘着テープ（ニットウ社製）を貼り付け、指圧でしごいて密着させ、その後、一気に剥がした。印刷像が残存しているかどうかを目視判定した。尚、粘着テープの貼り付け及び引き剥がしは、ＪＩＳ Ｋ５６００−５−６に準じて行った。判定基準として、「○」は、密着性が良好であり、実用上問題ないことを、「△」は、密着性がやや劣ることを、「×」は、印刷像が剥離したことを、それぞれ意味する。
（ｉｖ）傷付き性
印刷面に対し、爪先により引っ掻き、目視判定を行った。判定基準として、「○」は、傷が見られないことを、「△」は、若干傷が観察されることを、「×」は、傷が顕著であることを、それぞれ意味する。 About the obtained functional sheets (S8) to (S19), the printability was evaluated using the inks shown in Table 4. The results are shown in Table 5. Each evaluation method is as follows.
[Printability evaluation method]
Using the four types of ink shown in Table 4 (all manufactured by Toyo Ink Co., Ltd.), color-printed on the surface of the anchor coat layer of the functional sheet, and then placed in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% RH. It was allowed to stand for 24 hours. The printed surface was evaluated for the following adhesion and scratchability.

The conditions for color-expanding printing were as follows: the ink was solidified by irradiating 0.075 cc of ink on a RI tester quadrant roll, 1 air-cooled metal halide lamp at an output of 112 W / cm and a speed of 30 m / min.
(Iii) Adhesion (print fixability)
An adhesive tape (made by Nitto Co., Ltd.) having a width of 18 mm and a length of about 75 mm was affixed to the printing surface, and it was adhered with finger pressure and then peeled off at once. It was visually determined whether a printed image remained. The adhesive tape was attached and peeled according to JIS K5600-5-6. As a judgment criterion, “◯” indicates that the adhesion is good and that there is no problem in practical use, “△” indicates that the adhesion is slightly inferior, and “×” indicates that the printed image is peeled off. means.
(Iv) Scratch property The printed surface was scratched with a toe and visually judged. As a criterion, “◯” means that no flaw is observed, “Δ” means that a slight flaw is observed, and “x” means that the flaw is remarkable.

Comparative Example 3
Using the film (F1) in Table 3, functional sheets (S20) to (S23) were produced and evaluated in the same manner as in Example 2. The results are also shown in Table 5.

4). Production and evaluation of functional sheets (III)
Example 3
On the corona-treated surface of the corona-treated film of Example 1 (1) in Table 3, the following matting anchor coat compositions [ac5], [ac6], [ac7] and [ac8] were applied to bar coater # 5 and The functional sheets (S24) to (S31) were obtained by coating with # 10 and drying in an oven at 80 ° C. for 3 minutes to form an anchor coat layer.

[Ac5]; Emulsion (trade name “Cybinol PG”, trade name “Takelac XW-725-B186C”, manufactured by Mitsui Takeda Chemical Co., Ltd., solid content concentration 50%) and acrylic copolymer particles -4 ", manufactured by Seiden Chemical Co., Ltd., solid content concentration 34%), ion-exchanged water, and isopropyl alcohol were mixed at a pure content ratio of 100/147/280/120.
[Ac6]; polyurethane resin aqueous dispersion (trade name “Takelac XW-725-B186C”, manufactured by Mitsui Takeda Chemical Co., Ltd., solid content concentration 50%), copolymer having 90% or more of styrene units and 10% or less of acrylic units Emulsions containing particles (trade name “Cybinol PG-1”, manufactured by Seiden Chemical Co., Ltd., solid content concentration 49%), ion-exchanged water, and isopropyl alcohol are mixed at a pure fraction ratio of 100/102/280/120. Prepared.
[Ac7]; An acrylic copolymer emulsion (trade name “MK-100W”, manufactured by Shin-Nakamura Chemical Co., Ltd., solid content concentration 36.5%) and an emulsion containing acrylic copolymer particles (trade name “Cybinol PG”) -4 ", manufactured by Seiden Chemical Co., Ltd., solid content concentration 34%), ion-exchanged water, and isopropyl alcohol were mixed at a pure content ratio of 100 / 107.3 / 185.5 / 79.5. .
[Ac8]; acrylic copolymer emulsion (trade name “MK-100W”, manufactured by Shin-Nakamura Chemical Co., Ltd., solid content concentration of 36.5%), copolymer having styrene units of 90% or more and acrylic units of 10% or less The emulsion containing the particles (trade name “Cybinol PG-1”, manufactured by Seiden Chemical Co., Ltd., solid content concentration 49%), ion-exchanged water, and isopropyl alcohol are used in a pure fraction ratio of 100 / 74.3 / 185.5 / Prepared by mixing at 79.5.

About the obtained functional sheet (S24)-(S31), the glossiness in the surface of an anchor coat layer and the thermal contraction rate of a functional sheet were evaluated. The results are shown in Table 6. The glossiness evaluation method is as follows.
(V) Glossiness Using a digital gloss meter (model “GM-26D”, manufactured by Murakami Color Research Laboratory Co., Ltd.), the glossiness was measured by a method based on ISO 2813 conformity (JIS Z8741) for 60-degree specular gloss measurement.

  Furthermore, with respect to the functional sheets (S25), (S27), (S28) and (S30), an ink (trade name “UV161”) manufactured by T & K TOKAI is used in accordance with JIS K5600, and an anchor coat layer at 25 ° C. The surface was subjected to UV printing (ink stock 0.175 cc / 2sp), and the adhesion was evaluated in the same manner as the adhesion (iii) in Example 2. The ultraviolet irradiation conditions were an output of 120 W / cm and a speed of 50 m / min, and this was performed twice. The results are also shown in Table 6.

  The functional sheet of the present invention is a daily miscellaneous goods; corridors, ceilings, floors, kitchens, bathroom walls, etc. in buildings such as houses; various furniture; decorative sheets, pressure-sensitive adhesive sheets, laminate films used in various electric products, etc. Suitable for masking film, printing sheet, protective film, wallpaper and the like.

It is a schematic sectional drawing which shows an example of a functional sheet. It is a schematic sectional drawing which shows the other example of a functional sheet. It is a schematic sectional drawing which shows an example of the laminated type functional sheet which has a matte layer.

Explanation of symbols

1 and 1 '; Functional sheet 11; Thin body 12, 12a and 12b; Corona treatment layer 13; Anchor coat layer 14; Matte layer 2;

Claims (12)

  A thin-walled body made of an acrylic rubber-reinforced resin composition, a corona-treated layer formed on at least one surface of the thin-walled body, and an anchor coat layer disposed on the surface of the corona-treated layer Functional sheet.   The acrylic rubber reinforced resin composition is obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber polymer having a volume average particle diameter of 60 to 500 nm. The rubber-reinforced vinyl resin (A1) or a mixture of the rubber-reinforced vinyl resin (A1) and a (co) polymer (A2) of a vinyl monomer and having a graft ratio of 20 The functional sheet according to claim 1, comprising ˜170% acrylic rubber-reinforced resin.   The acrylic rubber-reinforced resin composition contains a grafted acrylic rubbery polymer, and contains an acrylic rubber-reinforced resin containing a unit made of an aromatic vinyl compound and a unit made of a vinyl cyanide compound. The acrylic rubber-reinforced resin has a graft ratio of 20 to 170%, the grafted acrylic rubbery polymer has a number average particle size of 60 to 200 nm, and has an intrinsic viscosity of acetonitrile-soluble component. 0.4 to 0.8 dl / g, the amount of bound vinyl cyanide compound in the acetonitrile-soluble component is 3 to 40% by mass, and the amount of bound vinyl cyanide compound measured by liquid chromatography is The functional sheet according to claim 1, wherein the standard deviation of the distribution is 5 or less.   The functional sheet according to any one of claims 1 to 3, wherein the thickness is 30 to 500 µm.   5. The thermal shrinkage rate (based on JIS K7133, rough condition adjustment at a temperature of 80 ° C. for 30 minutes) is 1% or less in the vertical direction and 1% or less in the horizontal direction. Functional sheet described in 1.   The functional sheet according to any one of claims 1 to 5, wherein a wetting index (based on JIS K6768) on the surface of the corona-treated layer is 40 mN / m or more.   The anchor coat layer is a modified olefin composition, polyester composition, acrylic composition, polyurethane composition, isocyanate composition, polyethyleneimine composition, polyamide composition, maleic acid composition, acetic acid. The functional sheet according to any one of claims 1 to 6, comprising at least one selected from a vinyl composition, a polyvinyl butyral composition, a natural rubber composition, and a synthetic rubber composition.   The functional sheet according to claim 1, wherein the anchor coat layer has a thickness of 0.01 to 10 μm.   The functional sheet according to any one of claims 1 to 8, wherein a surface of the anchor coat layer has a matte property.   A method in which the matte property includes at least one kind of fine particles selected from a polymer and an inorganic compound in the anchor coat layer, or a method in which a matte layer containing the fine particles is provided on the surface of the anchor coat layer, Or the functional sheet of Claim 9 obtained by the method of combining this method.   The functional sheet according to claim 10, wherein the matte layer has a thickness of 0.5 to 10 μm.   It is a manufacturing method of the functional sheet of any one of Claims 1 thru | or 8, Comprising: At least one surface of the thin-walled body consisting of an acrylic rubber reinforced resin composition is subjected to corona treatment to form a corona treatment layer. The corona treatment step, and the surface of the corona treatment layer is water-based and modified olefin-based composition, polyester-based composition, acrylic-based composition, polyurethane-based composition, isocyanate-based composition, and polyethyleneimine-based composition. At least one anchor coat composition selected from the group consisting of a rubber composition, a polyamide composition, a maleic acid composition, a vinyl acetate composition, a polyvinyl butyral composition, a natural rubber composition, and a synthetic rubber composition. And a coating process for coating. A method for producing a functional sheet.

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