JP2009226670A - Face material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a face material which is formed by laminating a thin body A and a base material B of a rubber-reinforced resin composition, has a good appearance of the thin part A, high adhesion between each layer, and a highly solvent-resistant anchor coat layer, and is easily manufactured. <P>SOLUTION: The face material is formed by laminating the thin body A 10 formed by molding a rubber-reinforced resin composition on at least one surface of the base material B 20, forming a corona-processed layer 10a formed by processing the surface with corona on the surface of thin body A 10 opposite the base material B 20, laminating an anchor coat layer 13 on the corona-processed layer 10a, and laminating a pattern layer 15 on at least a part of the anchor coat layer 13. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a face material excellent in design, which is suitably used as a member visually observed in various products. Specifically, it consists of a laminate of a thin-walled body of a rubber-reinforced resin composition and a substrate, and the thin-walled body has a pattern layer and is excellent in adhesion between each layer and solvent resistance of the anchor coat layer. The present invention relates to a face material having a good appearance and easy to manufacture.

Conventionally, a method of laminating a design layer on the surface of an ABS resin film is performed by thermally laminating a transfer film made of a PET film having a design layer on the surface in advance to the ABS film, and transferring the design layer to the ABS film. It is performed by peeling the PET film (see Patent Document 1). However, this method requires a process of transferring the pattern layer and peeling off the transfer film, which makes the manufacturing process complicated, and the transfer film becomes waste, which increases costs, and further, foreign substances are not generated in the manufacturing process. There is a risk of mixing into the laminate. Therefore, it is desired to form a design layer on the ABS resin film by a method such as direct printing.
Patent Document 2 describes a face material having a pattern layer.

  However, rubber reinforced resins such as ABS and ASA resin have low solvent resistance, and it is difficult to print directly on the surface of the resin. In addition, according to the experiments of the present inventors, when printing is directly performed on the rubber reinforced resin film, the solvent in the printing ink penetrates the rubber reinforced resin film, causing defects such as swelling on the back side of the print, The appearance of was inferior. Further, when a transparent resin layer is laminated on the printed surface, the appearance may be impaired, for example, bubbles are generated in the transparent resin layer.

JP 2005-178276 A JP 2006-034854 A

  The present invention is a face material comprising a laminate of a base material (B) and a thin-walled body (A) of a rubber-reinforced resin composition, and having a design layer on the surface of the thin-walled body (A), and the adhesion between each layer The object of the present invention is to provide a face material that has a good appearance of the design layer and is easy to manufacture. Furthermore, when a transparent resin layer is laminated | stacked as the uppermost layer on the opposite side to a base material (B), it aims at provision of the face material which the bubble generation etc. did not generate | occur | produce in a transparent resin layer but the external appearance of the transparent resin layer was excellent.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors, as a result, the thin-walled body (A) laminated on the base material (B) corona-treated the surface of the thin-walled body (A), and the corona-treated By forming an anchor coat layer on the surface and applying the design layer to the anchor coat layer, the appearance of the design layer can be improved, and further, by forming the anchor coat layer with a specific resin, adhesion between each layer It has been found that the properties are further improved and the appearance of the design layer can be further improved, and the present invention has been completed.

That is, according to the present invention, a thin-walled body (A) formed by molding a rubber-reinforced resin composition is laminated on at least one surface of the base material (B). A corona-treated layer formed by corona-treating the surface on the surface opposite to the base material (B), an anchor coat layer formed by laminating on the corona-treated layer, and at least a part of the anchor-coat layer. A face material is provided which is provided with a laminated design layer in order.
Since the pattern layer can be directly printed on the anchor coat layer on the surface opposite to the base material (B) of the thin-walled body (A) of this face material, the production is easy, such as a transfer film. Can be produced at low cost without producing any waste.
Further, as a preferred embodiment of the present invention, when the transparent resin layer is heat laminated, the residual solvent penetrates into the thin body (A) from the pattern layer, and the thin body (A) is swollen to cause the printed surface to be Phenomena such as poor appearance and the generation of bubbles in the transparent resin layer are suppressed, so the appearance is good.

According to a preferred embodiment of the present invention, the anchor coat layer is formed from at least one selected from the group consisting of a urethane resin (a1) and a polyester resin (a2).
More preferably, the anchor coat layer has a urethane resin (a1) of 60 to 10% by mass and a polyester resin (a2) of 40 to 90% by mass (provided that the component (a1) and The sum of component (a2) is 100% by mass). This anchor coat layer is more excellent in adhesion between the anchor coat layer and other layers. At the same time, the residual solvent from the design layer is prevented from penetrating into the thin body (A), and as a result, the appearance of the design layer and the transparent resin layer is improved.

  According to a further preferred embodiment of the present invention, the anchor coat layer is formed of at least one selected from the group consisting of a urethane resin (a1) aqueous dispersion and a polyester resin (a2) aqueous dispersion. It is formed as a coating layer. When this anchor coat agent is used, the anchor coat layer is excellent in formability.

  According to an even more preferred embodiment of the present invention, the urethane resin (a1) aqueous dispersion and the polyester resin (a2) aqueous dispersion are each an acrylic-modified urethane resin aqueous dispersion, And an acrylic-modified polyester resin aqueous dispersion. When this anchor coat agent is used, the anchor coat layer is excellent in formability and the adhesion between the layers is further improved.

The face material of the present invention is formed by laminating a thin-walled body (A) formed by molding a rubber-reinforced resin composition on at least one surface of the base material (B). In the thin-walled body (A), On the surface opposite to the base material (B), a corona treatment layer obtained by corona treatment of the surface, an anchor coat layer laminated on the corona treatment layer, and laminated on at least a part of the anchor coat layer Therefore, the pattern layer can be formed by printing directly on the anchor coat layer, which is easy to manufacture and can be manufactured at low cost without generating waste such as a transfer film. And the adhesiveness between each layer and the external appearance of a design layer are excellent.
Further, as a preferred embodiment, when the transparent resin layer is laminated on the design layer by thermal lamination, the residual solvent is prevented from penetrating from the design layer to the thin body (A), and the thin body (A) is formed. Phenomena such as blistering and the occurrence of bubbles in the transparent resin layer are suppressed, and the appearance is excellent.
Furthermore, when the anchor coat layer is formed of a specific resin, the adhesion between the layers provided on the surface of the thin-walled body (A) on the side opposite to the base material (B) is further improved.

The present invention will be described in detail below. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.

Fig.1 (a) shows the face material of embodiment of this invention. The illustrated face material is formed by laminating a thin-walled body (A) 10 formed by molding a rubber-reinforced resin composition on at least one surface of a base material (B) 20. The thin-walled body (A) 10 includes a corona-treated layer 10a formed by corona-treating the surface on the surface opposite to the base material (B) 20, and an anchor coat layer formed by laminating the corona-treated layer 10a. 11 and a pattern layer 13 laminated in order on at least a part of the anchor coat layer 11. Further, a transparent resin layer 15 is coated as the uppermost layer of each of these layers. Moreover, the 2nd thin body (C) 30 which consists of a resin composition containing a rubber reinforced resin is provided on the other surface of the base material (B).
FIG. 1A shows a configuration example. For example, a configuration in which the transparent resin layer 15 and / or the second thin-walled body (C) is omitted is also possible (see FIG. 1B).
Hereinafter, each layer will be described in detail.

1. Thin body (A) 10:
The thin-walled body (A) 10 is formed by molding a rubber-reinforced resin composition. The rubber-reinforced resin composition constituting the thin-walled body (A) 10 is a rubber-reinforced vinyl resin (A1) obtained by polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a), And if desired, it contains a rubber-reinforced resin made of (co) polymer (A2) obtained by polymerizing vinyl monomer (b) in the absence of rubbery polymer.

1-1. Rubber polymer (a):
The rubber polymer (a) is not particularly limited, and examples thereof include conjugated diene rubber polymers and non-conjugated diene rubber polymers. Examples of the conjugated diene rubbery polymer include polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, and hydrogenated products thereof. Examples of the nonconjugated diene rubbery polymer include ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, ethylene / butene-1 copolymer, ethylene / butene-1 / nonconjugated diene copolymer. Examples thereof include ethylene / α-olefin copolymer rubbers such as polymers; acrylic rubbers; silicone rubbers; silicone / acrylic IPN rubbers. These can be used individually by 1 type or in combination of 2 or more types.

  Among these rubber polymers (a), in the present invention, conjugated diene rubber polymers and acrylic rubbers are preferable, and acrylic rubbers are particularly preferable from the viewpoint of adhesion between the respective layers. In this specification, the rubber-reinforced resin composition using acrylic rubber is referred to as “acrylic rubber-reinforced resin composition”.

  The acrylic rubber is a polymer containing a (meth) acrylic acid alkyl ester as a monomer component, and is preferably a (co) (meth) acrylic acid alkyl ester (m1) (copolymer) having an alkyl group having 1 to 12 carbon atoms. ) A polymer, and more preferably a copolymer containing (meth) acrylic acid alkyl ester (m1) and polyfunctional vinyl compound (m2) as monomer components.

  (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 (m2) 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 Ester; (Meth) acrylic acid ester of polyhydric alcohol 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.

The acrylic rubber contains, in addition to the (meth) acrylic acid alkyl ester (m1) and the polyfunctional vinyl compound (m2), as a monomer component, another compound (m3) copolymerizable therewith. May be.
As said other compound (m3), a monofunctional aromatic vinyl compound, a diene compound, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

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 individually by 1 type or in combination of 2 or more types.

  The content of the (meth) acrylic acid alkyl ester (m1), the polyfunctional vinyl compound (m2) and the other compound (m3) in the acrylic rubber is preferably 80 to 99.99 mass in this order. %, 0.01 to 5% by mass and 0 to 19.99% by mass, more preferably 90 to 99.9% by mass, 0.1 to 2.5% by mass and 0 to 9.9% by mass. Yes (however, the sum of these three is 100% by mass).

The acrylic rubber can be produced by a polymerization method such as emulsion polymerization according to a conventional method.
The volume average particle diameter of the acrylic rubber 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, the shape stability and strength are excellent even in the case of a thin body having a small film thickness. The volume average particle diameter of the acrylic rubber can be measured by a dynamic light scattering method.
The volume average particle diameter of the acrylic rubber is the type and amount of the emulsifier, the type and amount of the polymerization initiator, the polymerization rate (polymerization temperature, method for adding the polymerization initiator, etc.) during the production of the acrylic rubber. In addition, it can be adjusted by appropriately selecting the stirring speed and the like.
The said acrylic rubber can be used individually by 1 type or in combination of 2 or more types.

The gel content of the 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 rubbery polymer is put into 20 ml of acetone (acetonitrile in the case of acrylic rubber) and stirred at 1,000 rpm for 2 hours under a temperature condition of 25 ° C. Thereafter, a centrifuge (rotational speed; 22,000 rpm) 1 hour and centrifuged at weighing the insoluble fraction obtained by separating the insoluble matter and the soluble matter (. The mass and _{W 1} grams), 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 monomer, 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. .

1-2. Vinyl monomer (b):
As the vinyl monomer (b), an aromatic vinyl compound and a vinyl cyanide compound are preferably used.

  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, other compounds copolymerizable with these may be used as the vinyl monomer. Examples of other compounds include (meth) acrylic acid esters, maleimide compounds, and other functional group-containing unsaturated compounds. Examples of the other functional group-containing unsaturated compounds include unsaturated acids, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, and acid anhydride group-containing unsaturated compounds. It is done. These can be used individually by 1 type or in combination of 2 or more types.

(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 individually by 1 type or in combination of 2 or more types. 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 individually by 1 type or in combination of 2 or more types.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used individually by 1 type or in combination of 2 or more types. 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 individually by 1 type or in combination of 2 or more types.

  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 individually by 1 type or in combination of 2 or more types.

Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  The vinyl monomer (b) is selected depending on the purpose, application, etc., and the type and amount used. When aromatic vinyl compounds and vinyl cyanide compounds are mainly used, The total amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the vinyl monomer (b). 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, more preferably 55 to 80% by mass, when the total of these is 100% by mass. % And 20 to 35% by mass.

1-3. Method for producing rubber-reinforced resin composition:
The rubber-reinforced resin composition contains the following component (A1) and optionally the following component (A2).

Component (A1): A rubber-reinforced vinyl resin obtained by polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a).
Component (A2): (co) polymer obtained by polymerizing vinyl monomer (b) in the absence of rubbery polymer (a).

  The rubber-reinforced vinyl resin (A1) usually includes a graft copolymer in which a (co) polymer of the vinyl monomer (b) is grafted to the rubber polymer (a), and a rubber weight A (co) polymer of the vinyl monomer (b) not grafted to the coalescence (a) is included. However, the rubber-reinforced vinyl resin (A1) may contain a rubbery polymer (a) in which the (co) polymer of the vinyl monomer (b) is not grafted.

  The method for producing the rubber-reinforced vinyl resin (A1) is not particularly limited, and examples thereof include known polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization, and suspension polymerization. Of these, emulsion polymerization is preferred. In addition, the usage-amount of a rubber-like polymer (a) and a vinyl-type monomer (b), When these sum total is 100 mass%, Preferably they are 5-70 mass% and 30-95 mass%, respectively. 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 polymerization initiators, cumene hydroperoxide, diisopropylbenzene hydroperoxide, benzoyl peroxide, lauroyl peroxide, potassium persulfate, azobisisobutyronitrile, tert-butylperoxylaurate, tert-butylperoxymono And carbonate. These can be used individually by 1 type or in combination of 2 or more types.
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.

As emulsifiers, alkyl sulfonates such as alkane sulfonate, alkyl benzene sulfonate, and alkyl naphthalene sulfonate; gum rosin, wood rosin, tall oil rosin, disproportionated rosin obtained by disproportionating these, 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 0.1-5 mass parts normally, when the whole quantity of the said vinylic monomer (b) is 100 mass parts, Preferably it is 0.1-3 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, terpinolene, etc. Is mentioned. These can be used individually by 1 type or in combination of 2 or more types. 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 (b) is 100 mass parts, Preferably it is 0.05-3 mass parts. is there.

  The polymerization temperature when the rubber-reinforced vinyl resin (A1) is produced by emulsion polymerization is usually 30 to 95 ° C, preferably 40 to 90 ° C. In order to recover the rubber-reinforced vinyl resin (A1) from the latex obtained by emulsion polymerization, usually inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride; sulfuric acid, hydrochloric acid, acetic acid, citric acid, malic acid, etc. This is done by adding a coagulant such as an acid. 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; a ketone such as methyl ethyl ketone; an inert polymerization solvent such as acetonitrile, dimethylformamide, or N-methylpyrrolidone; Polymerization may be performed in the presence of an initiator, or thermal polymerization may be performed in the absence of a polymerization initiator.

  The residual amount of the vinyl monomer remaining in the rubber-reinforced vinyl resin (A1) obtained by the above method is usually 10,000 ppm or less, preferably 5,000 ppm or less.

  The rubber-reinforced resin composition of the present invention may be composed of only one type of rubber-reinforced vinyl resin (A1) or may be composed of two or more types of rubber-reinforced vinyl resin (A1). .

Further, as described above, the rubber-reinforced resin composition of the present invention may be only the rubber-reinforced vinyl resin (A1), the rubber-reinforced vinyl resin (A1), and the vinyl monomer (b). It may be a mixture with the (co) polymer (A2) obtained by polymerization.
As the vinyl monomer (b) constituting the (co) polymer (A2), any of those described above can be used. The vinyl monomer (b) constituting the (co) polymer (A2) is a compound of the same type as the vinyl monomer (b) used for forming the rubber-reinforced vinyl resin (A1). It 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.

  The (co) polymer (A2) can be produced in the same manner as the production method of the rubber-reinforced vinyl resin (A1) except that the rubbery polymer (a) is not used. Specifically, It can be obtained by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like.

1-4. Physical properties of rubber-reinforced resin composition:
The graft ratio of the rubber-reinforced vinyl resin (A1) is preferably 20 to 170%, more preferably 20 to 150%, 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 rubber-reinforced vinyl resin (A1) may increase, and it may be difficult to reduce the thickness.
In addition, the graft ratio of the rubber-reinforced vinyl resin (A1) includes the type and amount of chain transfer agent used at the time of production, the type and amount of polymerization initiator, and the method and addition of monomer components during polymerization. It can adjust by selecting time etc. suitably.

In addition, the said graft ratio can be calculated | required by following formula (1).
Graft ratio (mass%) = {(S−T) / T} × 100
(1)
In the above formula, S represents 1 gram of rubber-reinforced vinyl resin in 20 ml of acetone (acetonitrile when the rubbery polymer is an acrylic rubber) and shakes with a shaker for 2 hours at 25 ° C. After that, the mixture was centrifuged for 4 hours with a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C., and the insoluble matter mass (g) obtained by separating the insoluble matter and the soluble matter was obtained. Yes, T is the mass (g) of the rubbery polymer contained in 1 gram of rubber-reinforced vinyl resin. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a 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 rubber-reinforced vinyl resin (A1) soluble in acetone (acetonitrile when the rubbery polymer is an acrylic rubber) is preferably 0.00. It is 2-1.0 dl / g, More preferably, it is 0.4-0.8 dl / g, More preferably, it is 0.4-0.7 dl / g. When the above intrinsic viscosity is within this range, it is easy to form a thin body.
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 0.00. 9 dl / g.

The intrinsic viscosity [η] was measured by the following method. First, the soluble component of the rubber-reinforced vinyl resin (A1) or the (co) polymer (A2) was dissolved in methyl ethyl ketone, and five different concentrations were prepared. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
The intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.

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

1-5. Preferred rubber-reinforced resin composition:
The rubber-reinforced resin composition of the present invention is preferably a rubber obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber (a). It consists of a reinforced vinyl resin (A1) or a mixture of this rubber reinforced vinyl resin (A1) and a (co) polymer (A2) of a vinyl monomer (b) and has a graft ratio of 20 to 170% resin.

The shape of the acrylic rubber (a) dispersed in the acrylic rubber-reinforced resin composition is not limited, and may be either regular or irregular. 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. The number average particle diameter of the acrylic rubber dispersed in the acrylic rubber-reinforced resin composition is determined by immersing a thin piece prepared from the thin-walled body (A) according to the present invention in a solution of OsO ₄ or RuO _4. After dyeing, it is observed with a transmission electron microscope, and can be, for example, the average value of the particle diameters measured for 100 grafted acrylic rubber particles.

  The amount of bound vinyl cyanide compound (hereinafter also referred to as “bound VC amount”) of the acetonitrile-soluble component of the acrylic rubber-reinforced resin composition is preferably 3 to 40% by mass, more preferably 10 to 30%. % By mass. 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 be obtained by liquid chromatography.

More preferably, the acrylic rubber-reinforced resin composition is a resin including a unit composed of an aromatic vinyl compound and a unit composed of a vinyl cyanide compound, and has a graft ratio of 20 to 170%. The acrylic rubber dispersed in the reinforced resin composition has a number average particle diameter of 60 to 200 nm, an intrinsic viscosity of acetonitrile-soluble component of 0.4 to 0.8 dl / g, and the above-mentioned acetonitrile-soluble component bonded cyanide. This resin is a resin having an amount of vinyl chloride compound of 3 to 40% by mass and a standard deviation of the distribution of the above-mentioned bound vinyl cyanide compound amount measured by liquid chromatography of 5 or less. The graft ratio is preferably 20 to 170%, more preferably 20 to 150%, and still more preferably 30 to 150%. The number average particle diameter is preferably 50 to 500 nm, more preferably 60 to 180 nm, and still more preferably 70 to 150 nm. The intrinsic viscosity is preferably 0.2 to 1.0 dl / g, more preferably 0.4 to 0.8 dl / g, and still more preferably 0.4 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 acrylic rubber-reinforced resin composition according to the present invention may further contain 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 singly 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 individually by 1 type or in combination of 2 or more types.
Content of the said ultraviolet absorber is 0.05-5 mass parts normally with respect to 100 mass parts of the said acrylic rubber reinforced resin composition whole.

Examples of the weathering agent include organic phosphorus compounds, organic sulfur compounds, and organic compounds containing a hydroxyl group. These can be used individually by 1 type or in combination of 2 or more types.
Content of the said weathering agent is 0.1-5 mass parts normally with respect to 100 mass parts of the said whole acrylic rubber reinforced resin composition.

Examples of the filler include talc, titanium oxide, clay, calcium carbonate and the like. These can be used individually by 1 type or in combination of 2 or more types.
Content of the said filler is 0.05-20 mass parts normally with respect to 100 mass parts of the said whole acrylic rubber reinforced resin composition.

1-6. Method for producing thin body (A) 10:
The thin-walled body (A) 10 can usually be produced by various molding methods such as calendar molding, inflation molding, T-die extrusion molding, etc., from the rubber-reinforced resin composition. 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 (A) 10 may be a smooth surface, and may have a regular pattern or an irregular pattern by hairline processing, embossing, etc.

Thermal contraction rate of the thin-walled body (A) 10 (JIS
According to K7133, temperature adjustment for 30 minutes at a temperature of 80 ° C. is preferably 1% or less in the longitudinal direction (flow direction of the thin body during production) and in the lateral direction (direction perpendicular to the flow direction of the thin body). 1% or less, more preferably 0.8% or less in the vertical direction and 0.8% or less in the horizontal direction. Therefore, when the anchor coat layer 11 is laminated and left at a high temperature, or when heating is involved in various printing techniques, the generation and deformation of wrinkles are suppressed, and good printability and appearance can be maintained. This heat shrinkage rate is the same when the corona treatment layer 10a is formed.

1-7. Corona treatment:
The thin-walled body (A) 10 is subjected to corona treatment on the surface opposite to the base material (B) 20. This corona treatment can be performed using a known corona treatment apparatus. The detailed method of the corona treatment is as described in the “corona treatment step” described later. The corona-treated surface 10a has functional groups such as> C = O and -COOH increased as compared with the untreated surface, and the wetting index according to JIS K6768 is usually 40 mN / m or more, Preferably it is 43 mN / m or more, More preferably, it is 45 mN / m or more. If the wetting index is too small, the anchor coat layer 11 may be peeled off.

The corona treatment is essential to be applied to the surface of the thin-walled body (A) 10 on the side where the anchor coat layer 11 is to be formed. In order to improve the adhesion with the base material (B) 20, The other surface can also be corona treated.
The corona-treated surface may be subjected to surface processing such as hairline processing or embossing.

2. Anchor coat layer 11:
An anchor coat layer 11 is provided on the surface of the thin-walled body (A) 10 opposite to the base material (B) 20, that is, the corona-treated surface 10a. The anchor coat layer 11 is formed as a resin layer containing a polymer as a main component. In addition, the anchor coat layer is used for the purpose of improving the strength, decorating, etc., as necessary, filler, metallic glossy particles, dispersant, antifoaming agent, viscosity adjusting agent, film-forming aid, pH adjusting agent. , Antiseptics, fungicides, UV absorbers, weathering agents, antioxidants, anti-aging agents, antistatic agents, flame retardants, antifogging agents, lubricants, antibacterial agents, tackifiers, plasticizers, colorants, etc. Can be included.

  Examples of the polymer that forms the anchor coat layer 11 include a modified olefin resin, a polyester resin, an acrylic resin, a urethane resin, an isocyanate resin, a polyethyleneimine resin, a polyamide resin, a maleic acid resin, Examples thereof include vinyl acetate resin, polyvinyl butyral resin, natural rubber, and synthetic rubber. These polymers can be used singly or in combination of two or more.

  Among these polymers, the anchor coat layer 11 in the present invention is preferably formed from at least one selected from the group consisting of a urethane resin (a1) and a polyester resin (a2). When these resin components are used, the anchor coat layer 11 and the corona-treated surface 10a, the pattern layer 13, and the transparent resin layer 15 are excellent in adhesion to the transparent resin layer 15. 11 is also excellent in printability (surface layer adhesion, pattern layer appearance, etc.).

  The anchor coat layer 11 can be usually produced as a coating layer using a dispersion in which the above polymer is dispersed in an appropriate solvent. As the dispersion, the thin-walled body (A) 10 is affected by the solvent. In order to prevent this, it is preferable to use an aqueous dispersion. The anchor coat layer 11 made of the polyester resin and / or the urethane resin is made of, for example, at least one selected from the group consisting of a urethane resin (a1) aqueous dispersion and a polyester resin (a2) aqueous dispersion. It can form easily as a formed coating-film layer.

  The urethane resin (a1) aqueous dispersion is preferably an acrylic modified urethane resin aqueous dispersion, and an acrylic modified urethane resin having a shell-core structure in which the acrylic component is a core and the urethane component is a shell. More preferably, it is an aqueous emulsion. Here, the acrylic modification means that the acrylic monomer or polymer is physically bonded to the urethane resin in addition to those in which the acrylic monomer or polymer is chemically bonded to the side chain or terminal of the urethane resin. To form a mixture or complex.

  The polyester resin (a2) aqueous dispersion is preferably an acrylic-modified polyester resin aqueous dispersion, and more preferably a polyester-acrylic composite aqueous dispersion. The polyester-acrylic composite aqueous dispersion may be in the form of an emulsion. Here, the acrylic modification means that the acrylic monomer or polymer is physically attached to the polyester resin in addition to the acrylic monomer or polymer chemically bonded to the side chain or terminal of the polyester resin. In which a mixture or a complex is formed by binding to.

  The urethane resin (a1) aqueous dispersion and the polyester resin (a2) aqueous dispersion may each be used alone, but are preferably used as an aqueous dispersion in which both are mixed. When both are mixed and used, the adhesion and appearance of each layer of the laminate of the present invention are excellent. The ratio when using the mixture of both is preferably 60 to 10% by mass of the urethane resin (a1) and 40 to 90% by mass of the polyester resin (a2) in terms of solid matter. a1) 50 to 10% by mass and 50 to 90% by mass of the polyester resin (a2) are more preferable, 40 to 10% by mass of the urethane resin (a1) and 60 to 90% by mass of the polyester resin (a2) ( However, the total of the component (a1) and the component (a2) is particularly preferably 100% by mass). Within this mixing ratio range, a laminate having an excellent balance between appearance and adhesion of each layer can be obtained.

  The anchor coat layer 11 can be formed as a coating film by applying the dispersion to the corona-treated surface 10a of the thin-walled body (A) 10 using an appropriate application means or printing means and drying it. Details of the method for forming the anchor coat layer 11 are as described in “Coating process” described later.

  The anchor coat layer 11 has a thickness of preferably 0.01 to 10 μm, more preferably 0.02 to 8 μm, still more preferably 0.05 to 7 μm, and particularly preferably 0.05 to 5 μm. Within this range, the object of the present invention can be achieved.

In the present invention, the thermal contraction rate (JIS) of the thin-walled body obtained by providing the anchor coat layer 11 on the corona-treated thin-walled body (A) 10.
K7133, temperature adjustment at 80 ° C. for 30 minutes) is preferably 1% or less in the vertical direction and 1% or less in the horizontal direction, more preferably 0.8% or less in the vertical direction, and It is 0.8% or less in the horizontal direction. In the range of this heat shrinkage rate, the deformation of the image of the design layer 13 formed on the surface of the anchor coat layer 11 can be satisfactorily suppressed, and the transparent resin layer 15 is applied to the surface of the design layer by a method such as thermal lamination. Even when laminated, the shape can be maintained stably.

3. Pattern layer 13:
A design layer 13 is provided on the surface of the anchor coat layer 11 formed on the corona-treated surface 10a of the thin-walled body (A) 10. The pattern layer 13 can be formed by directly printing (direct printing) on the anchor coat layer by various printing methods. Examples of the printing method include known printing methods such as offset printing, gravure printing, screen printing, and ink jet printing. The ink used for printing may be either water-based ink or non-water-based ink such as solvent-based ink. A solvent-based ink is preferred because of its excellent printability.

In the present invention, since the anchor coat layer 11 is formed on the thin-walled body (A) 10, the solvent component of the ink is prevented from penetrating to the thin-walled body (A) 10. This is convenient when the pattern layer 13 is formed. In particular, when the anchor coat layer 11 is formed from a mixture of the urethane resin (a1) and the polyester resin (a2), this effect is remarkable, which is preferable.
As another method, as described in JP-A-2005-178276, the design layer can be formed by a method of transferring a design from a PET film on which a design has been printed in advance to the anchor coat layer 11 of the present invention.

  As shown in FIG. 1, in the present invention, in the thin-walled body (A) 10, layers other than the design layer 13 are formed as continuous layers, whereas the design layer 13 is usually microscopically. Although it is formed as a layer separated into dots as seen, the pattern layer 13 may be formed as a continuous layer printed on the entire surface of the anchor coat layer 11.

4). Transparent resin layer 15:
If necessary, a transparent resin layer 15 is provided on the surface of the thin-walled body (A) 10 opposite to the base material 20 so as to cover the surface of the design layer 13 and the like.
The transparent resin layer 15 is usually made of a thermoplastic resin molding resin layer. The thermoplastic resin is not particularly limited as long as it is transparent. For example, acrylic resin, polycarbonate resin, polypropylene resin, polyethylene resin, polyester resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, polyamide resin are used. Resin, Tetrafluoroethylene resin, Tetrafluoroethylene-hexafluoropropylene copolymer resin, Tetrafluoroethylene-ethylene copolymer resin, Tetrafluoroethylene-Perfluorovinyl ether copolymer resin, Trifluoroethylene chloride resin Vinylidene fluoride resin, vinyl chloride resin and the like can be used. Among these thermoplastic resins, it is preferable to use an acrylic resin from the viewpoint of adhesion to the pattern layer 13 and the anchor coat layer 11. As the acrylic resin, those containing methyl methacrylate as a constituent monomer component are preferable.

  The transparent resin layer 15 can be laminated by thermally laminating the thermoplastic resin previously formed into a film shape or a sheet shape so as to cover the pattern layer 13. As another method, the thermoplastic resin may be used so as to cover the anchor coat layer 11 or the design layer 13 of a film or sheet formed by forming the anchor coat layer 11 and the design layer 13 on the thin body (A) 10. It can also be laminated by extrusion lamination.

  The thickness of the transparent resin layer 15 is preferably 20 μm to 2000 μm, more preferably 50 μm to 1500 μm, and preferably 50 μm to 1000 μm. If the thickness is less than 20 μm, surface roughness may occur due to the influence of the design layer 13. When this thickness exceeds 2000 micrometers, it will become economically disadvantageous.

5. Other details of thin body (A) 10:
In the present invention, the thin-walled body (A) 10 may be provided with an adhesive layer on the surface opposite to the anchor coat layer 11 of the thin-walled body (A) 10 in order to adhere to the base material (B) 20. At that time, in order to improve the adhesion between the thin-walled body (A) 10 and the adhesive layer, the smoothness of the adhesive layer, etc., the surface of the thin-walled body (A) 10 provided with the adhesive layer is subjected to corona treatment or primer treatment in advance. It may be left. The pressure-sensitive adhesive layer can be formed by directly applying a composition for forming a pressure-sensitive adhesive layer (pressure-sensitive adhesive composition) containing a polymer, a tackifier, a solid plasticizer, and the like to the surface and drying it. Release paper or the like may be provided on the outer surface of the adhesive layer. However, when the adhesive layer is a heat-sensitive adhesive layer, the release paper may not be provided.

6). Second thin body (C) 30:
The second thin-walled body (C) 30 is laminated in order to improve performances such as design properties, mechanical strength, scratch resistance, and hygiene.
The material of the second thin-walled body (C) 30 is not particularly limited, and examples thereof include the molding material of the base material (B) 20 shown above, and further, rubbery polymer, paper, cloth, etc. Can be mentioned. Preferably, it is a rubber reinforced resin such as ABS resin, AES resin, ASA resin, etc., and has excellent performance.
Examples of the second thin body (C) include a film or a sheet.

7). Preferred lamination method to the thin-walled body (A) 10:
In the present invention, the thin-walled body (A) 10 is formed with an anchor coat layer 11 by applying a corona treatment step for corona treatment of at least one surface and applying an aqueous polymer dispersion to the corona-treated surface 10a. And a decoration step of forming the pattern layer 13 by direct printing on the surface of the anchor coat layer 11, and if necessary, a transparent resin on the surface of the pattern layer 13 or the anchor coat layer 11 A laminating step for laminating the layer 15 is performed.

  In this preferred method, since the anchor coat layer 11 is formed as a coating film by applying an aqueous dispersion of a polymer, the solvent in the ink enters the thin body (A) 10 and the thin body (A) 10. Since the back surface of the film is not swollen, and the design layer is formed directly on the surface of the anchor coat layer 11, the waste of the transfer film as in the conventional transfer method is not generated and the environment is avoided. Furthermore, since a wide variety of printing inks and printing techniques including solvent ink can be used to form the pattern layer 13, the selection range of the pattern layer 13 is widened and various designs are possible.

  The corona treatment step is usually 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, ceramic) and a number of them. A corona discharge is generated by applying a high voltage to the electrodes arranged at intervals of mm, and the thin-walled body (A) 10 made of the rubber-reinforced resin composition is passed between the electrode and the roll during the discharge. Can be implemented. Here, the corona treatment may be performed on only one side of the thin-walled body (A) 10 or may be performed 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. The discharge amount as the processing condition is set as appropriate.
The amount of discharge is obtained by the following equation, where the length of the discharge electrode is L (m), the speed of the thin body (A) is V (m / min), and the discharge power is P (W).

Discharge amount = P / (L × V)

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 body (A) 10 to generate ozone O ₃ . 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 rubber-reinforced resin composition constituting the thin-walled body (A) 10 to form carbonyl C═O.

The coating process according to this method is carried out by applying an aqueous dispersion of a polymer to the surface 10a of the corona-treated thin-walled body (A) 10 formed by the corona treatment process using an appropriate coating method. it can.
As a solvent of this aqueous dispersion, water alone or a mixed medium containing water as a main component and at least one water-soluble organic solvent selected from alcohol, ester, ketone and ether as necessary is added. Is used.

  Examples of the polymer include modified olefin resins, polyester resins, acrylic resins, urethane resins, isocyanate resins, polyethyleneimine resins, polyamide resins, maleic resins, vinyl acetate resins, polyvinyl butyral resins. At least one selected from natural rubber, synthetic rubber and the like can be used. Preferred polymers are as described above for the anchor coat layer.

The aqueous dispersion is optionally filled with fillers, metallic glossy particles, dispersants, antifoaming agents, viscosity modifiers, film-forming aids, pH adjusters, preservatives, fungicides, UV absorbers, A weathering agent, an antioxidant, an anti-aging agent, an antistatic agent, a flame retardant, an antifogging agent, a lubricant, an antibacterial agent, a tackifier, a plasticizer, a colorant and the like may be contained.
The solid content concentration of the aqueous dispersion is usually 0.2 to 50% by mass, preferably 0.5 to 40% by mass.

The application method of the aqueous dispersion can be selected from general application methods such as a gravure coating method, a reverse coating method, a knife coating method, and a kiss coating method, depending on the type and viscosity of the composition.
In general, the coating step preferably includes a step of drying the coating film by heating or the like.
In addition, after forming the anchor coat layer 11 as described above, the surface of the anchor coat layer 11 may be subjected to a smoothing process, a glossing process, or the like, if necessary, with a calendar device or the like. Further, a primer layer or the like may be further laminated on the surface of the anchor coat layer 11.

  The said decoration process is implemented by providing the design layer 13 by direct printing on the surface on the opposite side to the base material layer (B) 20 of the anchor coat layer 11. In the present invention, since the anchor coat layer 11 is provided, the pattern layer 13 can be formed by various printing methods such as offset printing, gravure printing, screen printing, ink jet printing, and the ink used for printing is also water-based. Either an ink or a non-aqueous ink such as a solvent-based ink may be used.

  The laminating step is performed by laminating the transparent resin layer 15 over the entire surface of the design layer 13 opposite to the anchor coat layer 11. In this lamination step, for example, a transparent resin film or sheet molded in advance may be laminated by thermal lamination so as to cover the pattern layer 13 or the anchor coat layer 11, and the thin body (A) 10 may be anchor-coated. A thermoplastic resin can be laminated to the extrusion laminate so as to cover the design layer 13 of the film or sheet on which the layer 11 and the design layer 13 are formed.

8). Base material (B) 20:
Although the base material (B) 20 used by this invention will not be specifically limited if it can be laminated | stacked with the above-mentioned thin body (A) 10, As a molding material of the base material (B) 20, a thermoplastic resin, A thermosetting resin, an organic material, an inorganic material, etc. are mentioned.
Examples of the thermoplastic resin include polyvinyl chloride, polyethylene, polypropylene, AS resin, ABS resin, AES resin, ASA resin, polystyrene, high impact polystyrene, EVA, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polylactic acid. Etc. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the thermosetting resin include phenol resin, epoxy resin, urea resin, melamine resin, and unsaturated polyester resin. These can be used individually by 1 type or in combination of 2 or more types.
The thermoplastic resin and the thermosetting resin may be a recycled resin or a mixture of a recycled resin and a non-recycled resin.
The thermoplastic resin and thermosetting resin include glass fiber, carbon fiber, metal fiber, glass bead, wollastonite, glass milled fiber, glass flake, calcium carbonate, talc, mica, kaolin, graphite, wood powder, Fillers such as pulverized particles of a thermosetting resin can be blended singly or in combination of two or more.
The blending amount of the filler is usually 3 to 30 parts by mass per 100 parts by mass of the thermoplastic resin and the thermosetting resin.
In addition to the filler, an antioxidant, an antistatic agent, a lubricant, a colorant, a flame retardant, a flame retardant aid, and the like may be added to the thermoplastic resin and the thermosetting resin as necessary.
The thermoplastic resin and the thermosetting resin may be a foam molded article to which a foaming agent is added, and the expansion ratio is preferably 1.05 to 20 times, more preferably 1.2 to 15 times.
Examples of organic materials include insulation board, MDF (medium fiber board), hard board, particle board, lumbar core, LVL (single board laminate), OSB (orientation board), PSL (pararam), WB ( Wafer board), hard fiber board, soft fiber board, lumbar core plywood, board core plywood, special core-plywood, veneer core-plywood board, laminated sheet / board of paper impregnated with tap resin, fine (crushed) paper, etc. Examples include a board obtained by mixing an adhesive with a small piece / linear body and heating and compressing, various kinds of wood, and the like.
Examples of inorganic materials include calcium silicate board, flexible board, homo-cement board, gypsum board, sizing gypsum board, reinforced gypsum board, gypsum lath board, makeup gypsum board, composite gypsum board, iron, Examples include metals such as aluminum, copper, and various alloys.
When a metal is used as the base material (B) 20, many are used as a metal plate. As the metal plate, for example, a metal plate generally used as a base material for a resin-coated metal plate is used. Specifically, a hot dip galvanized steel plate, an electrogalvanized steel plate, an aluminum / zinc composite plated steel plate, Examples thereof include an aluminum plated steel plate, a stainless steel plate, and an aluminum alloy plate. These metal plates are not particularly limited with respect to thickness, heat treatment conditions, plating thickness, and the like, and the surface treatment of the metal plate may be subjected to phosphate treatment, chromate treatment, or the like.
The shape of the base material (B) 20 takes various shapes according to the use of the face material of the present invention, but is usually plate-shaped (the surface may not be flat, and there are deformations such as roundness and unevenness). And a molded body having a thickness greater than that of a plate.

9. Face material:
The face material of the present invention includes a corona-treated layer 10a, an anchor coat layer 11, a design layer 13, and a transparent resin as necessary on one surface of the base material (B) 20. It is obtained by laminating layers provided with the layer 15. Moreover, you may laminate | stack this thin body (A) 10 on the other surface of this base material (B) 20 as needed.
Moreover, this base material (B) 20 may be comprised by 1 layer or 2 layers or more. When composed of two or more layers, each layer may be composed of the same material, or may be composed of different materials.
The surface on which the thin-walled body (A) 10 is not laminated may be provided with a design and coloring in order to improve design properties.
Examples of the adhesion in the lamination of the thin-walled body (A) 10 and the base material (B) 20 include a method using an adhesive, a pressure-sensitive adhesive, and the like, and a method of heating and pressure bonding.
Further, in order to increase the adhesive strength, one or both of the bonding surfaces may be subjected to corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, UV treatment, ion bombardment treatment, electron beam treatment, solvent treatment, anchor as necessary. Processing such as coating may be performed.
By using the face material of the present invention as a member of various products, the design of the product can be improved at a lower cost than the conventional method. Furthermore, there is little deterioration of the pattern in long-term use, and it is excellent in durability.
The face material of the present invention can be used as a member for building products, electrical products, vehicle products, furniture products, kitchen products, and sundries products.
Specific members include, for example, furniture materials such as floor materials, wall materials, ceiling materials, door materials, chiffon materials, various handrails, table members, desk members, bookcases, window frames, tiles, gutters, deck materials. , Wood, exterior, sink, system kitchen, bed, staircase, wall panel, frame, pencil, brush, baseboard, curb, edge, chair, sash, parabolic antenna, bamboo fence, air conditioner duct cover It can be used for bathroom members, panel water tank members, signboards, display boards, guide boards, office supplies related fields, interior / exterior of vehicles, OA / home appliance parts.
Examples of the thin body (A) and thin body (C) designs of the present invention include coloring, marble patterns, wood grain patterns, embossed patterns, painting titles, characters, and the like.

  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 composition:
(1) Acrylic rubber reinforced resin (A1):
Solid content concentration 40% containing acrylic rubber 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. The latex was further diluted with 1 part sodium dodecylbenzenesulfonate and 150 parts ion-exchanged water. Thereafter, the inside of the reactor was replaced with nitrogen gas, 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 at 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. Thereafter, washing with water and drying were performed to obtain an acrylic rubber-reinforced vinyl resin.

(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 composition:
45 parts of the above rubber-reinforced vinyl resin (A1) and 55 parts of acrylonitrile / styrene copolymer (A2) are put into a Henschel mixer and mixed, and then the mixture is supplied to a twin screw extruder at a temperature of 200 to It was melt-kneaded at 240 ° C. to obtain pellets. The graft ratio of the obtained resin composition was 85%, the number average particle diameter of the grafted acrylic rubbery polymer was 110 nm, the intrinsic viscosity of acetonitrile soluble matter was 0.45 dl / g, the amount of bound VC (the amount of bound acrylonitrile) ) Is 24.0%.

2. Examples 1-4, Comparative Example 1:
(1) Manufacture of face materials:
The acrylic rubber-reinforced resin composition pellets prepared above were melted at 180 to 190 ° C. and further kneaded using a hot roll. Thereafter, the kneaded product was rolled using a calender device equipped with a calender roll adjusted to a temperature of 190 ° C. to produce a long thin body (A) 10 having a width of 1,000 mm and a thickness of 100 μm. This thin-walled body (A) 10 is allowed to stand in a dryer at a temperature of 80 ° C. for 30 minutes.
When the heat shrinkage rate was measured according to K7133, it was 0.2% in both the vertical and horizontal directions.

  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). Set the thin-walled body (A) 10 that has been cut into 3 mm so that the distance between the electrode and the thin-walled body (A) 10 is 3 mm, and perform corona treatment by changing the speed of the thin-walled body (A) 10 under the following conditions. It was. It was 54 mN / m when the wettability in the corona treatment surface of each thin body (A) 10 after a corona treatment was determined.

Corona treatment conditions:
Corona treatment density: 51 (W · min / m ² )
Discharge power: 100 (W)
Film speed: 7 (m / min)

The method for determining the wetting index is as follows. Mixture liquid for wet tension test (ethylene glycol monoethyl ether amide, manufactured by Wako Pure Chemical Industries, Ltd.) and cotton swab (trade name “HUBY-340
CA-002 cotton applicator "(manufactured by Sanyo Co., Ltd.) was applied to the corona-treated surface 10a of each thin-walled body (A) 10, and the wettability was determined according to JIS K6768.

  Next, an aqueous dispersion for anchor coat composed of the components shown in Table 1 was applied to the corona-treated surface 10a of each thin-walled body (A) 10 using a bar coater # 5, and dried in a dryer at 80 ° C. for 3 minutes. An anchor coat layer 11 having a thickness of 1.5 μm was formed.

About the thin-walled body in which the obtained anchor coat layer 11 was formed, the following anchor coat layer adhesion was evaluated. The results are shown in Table 1.
Further, printing is performed on the surface of the anchor coat layer 11 using a solvent-based ink under the drying temperature and printing speed conditions described in Table 1, and then left in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. A pattern layer was formed. The following adhesion was evaluated for this printed surface.
Furthermore, after obtaining a thin-walled body (A) 10 in which a transparent resin film 15 was formed by thermocompression bonding of the transparent resin film on the printed surface at 150 ° C., 20 kg / cm ² for 15 minutes, about the thin-walled body, Appearance and adhesion were evaluated as follows. As the transparent resin film, an acrylic resin film having a thickness of 125 μm and contained in a ratio of methyl methacrylate / butyl acrylate / styrene = 81/16/3 (mass ratio, total of three components is 100) was used.
Next, a face material was prepared using the thin-walled body (A) 10 on which the corona-treated layer 10a, the anchor coat layer 11, the design layer 13, and the transparent resin layer 15 were formed as described above, and the base material shown below.
The surface of the base material (B) 20 of the base material composed of the base material (B) 20 and the base material (C) 30 shown in the figure, and the surface opposite to the transparent resin layer 15 etc. of the thin-walled body (A) 10 And an adhesive composition of BA-20 / BA-11B = 100 / 2.5 (parts) [both trade names, manufactured by Chuo Rika Kogyo Co., Ltd.], an application amount of 80 g / m ² (dry ), Room temperature (25 to 30 ° C.), and 0.5 N / cm ² × 2 day pressing conditions to obtain a face material (system kitchen door).
The material of the substrate (B) 20 is MDF, and the size is 15 mm thick, 297 mm long, and 210 mm wide.
The material of the base material (C) 30 is Valuetech NSG100 (trade name, manufactured by Techno Polymer Co., Ltd.). The size is 0.5 mm thick, 297 mm long, and 210 mm wide. The color is colored with titanium oxide and white.
Bonding of the base material (B) 20 and the base material (C) 30 was performed under the above-described bonding conditions.
In addition, Comparative Example 1 was manufactured and evaluated in the same manner as described above except that the thin-walled body (A) 10 was not subjected to corona treatment and the anchor coat layer 11 was not formed.

(2) Evaluation:

(I) Appearance of printed surface:
The swollen print surface was visually observed and evaluated according to the following criteria.
○: No abnormality
Δ: Slightly swollen,
×: Remarkable swelling.

(Ii) Anchor coat layer adhesion:
An adhesive tape having a width of 18 mm and a length of about 75 mm was affixed to the surface of the anchor coat layer 11 and adhered with finger pressure, and then peeled off at once. Whether or not the anchor coat layer 11 remained was visually observed and judged according to the following criteria. The adhesive tape can be attached and peeled off according to JIS.
It carried out according to K5600-5-6.
○: Adhesion is good and there is no practical problem.
Δ: Adhesion is slightly inferior,
X: The anchor coat layer 11 is peeled off.

(Iii) Print surface adhesion:
An adhesive tape having a width of 18 mm and a length of about 75 mm was affixed to the printed surface of the pattern layer 13 and adhered with finger pressure, and then peeled off at once. Whether the pattern layer 13 remained or not was visually observed and judged according to the following criteria. The adhesive tape can be attached and peeled off according to JIS.
It carried out according to K5600-5-6.
○: Adhesion is good and there is no practical problem.
Δ: Adhesion is slightly inferior,
X: The design layer is peeled off.

(Iv) Transparent resin layer appearance:
The appearance of the transparent resin layer 15 was visually observed and evaluated according to the following criteria.
Evaluation criteria ○: No bubbles are observed in the transparent resin layer 15.
X: Air bubbles are observed in the transparent resin layer 15.
(V) Adhesiveness of transparent resin layer The transparent resin film was cut with an X mark with a cutter, and the adhesiveness between the printed surface and the film was evaluated according to the following criteria.
Evaluation standard (circle): A cut end does not peel but it has adhered.
Δ: A part of the cut surface was peeled off.
X: It peeled over the whole surface of a cut end.

The abbreviations shown in Table 1 have the following meanings.
A-215GE: Pesresin A-215GE (trade name; manufactured by Takamatsu Yushi Co., Ltd., polyester-acrylic composite aqueous dispersion).
SU-100: Rikabond SU-100 (trade name; manufactured by Chuo Rika Kogyo Co., Ltd., an acrylic-modified urethane resin aqueous emulsion having a shell-core structure with an acrylic component as a core and a urethane component as a shell).
ES-90: Rikabond ES-90 (trade name; manufactured by Chuo Rika Kogyo Co., Ltd., aqueous acrylic particle emulsion).

Table 1 shows the following.
The face materials of Examples 1 to 4 provided with the anchor coat layer 11 are excellent in printing surface adhesion, transparent resin layer appearance, transparent resin layer adhesion, anchor coat layer adhesion, and printing surface appearance. On the other hand, in Comparative Example 1 in which the anchor coat layer 11 was not provided, bubbles were generated in the transparent resin layer, and not only the appearance of the transparent resin was inferior but also the appearance of the printed surface was inferior.

By using the face material of the present invention as a member of various products, the design of the product can be improved at a lower cost than the conventional method. Furthermore, there is little deterioration of the pattern in long-term use, and it is excellent in durability.
The face material of the present invention can be used as a member for building products, electrical products, vehicle products, furniture products, kitchen products, and sundries products.

It is a cross-sectional schematic diagram which shows an example of the face material of this invention, (a) shows the case where the transparent resin layer 15 and the 2nd thin body (C) 30 are provided, (b) is not provided.

Explanation of symbols

10 Thin body (A)
10a Corona-treated surface of thin-walled body (A) (corona-treated layer)
11 Anchor coat layer 13 Design layer 15 Transparent resin layer 20 Base material (B)
30 Second thin body (C)

Claims (9)

A thin-walled body (A) formed by molding a rubber-reinforced resin composition is laminated on at least one surface of the substrate (B),
The thin-walled body (A) includes a corona-treated layer formed by corona-treating the surface on the surface opposite to the substrate (B), an anchor coat layer formed by laminating the corona-treated layer, the anchor A pattern layer formed by laminating at least part of the coat layer is provided in order,
A face material characterized by that. In claim 1,
The thin-walled body (A) is further formed by coating a transparent resin layer as the uppermost layer of each layer formed on the surface opposite to the base material (B).
A face material characterized by that. In claim 1 or claim 2,
The rubber reinforced resin composition forming the thin body (A) is a rubber reinforced resin composition containing an acrylic rubber reinforced resin.
A face material characterized by that. In any one of Claims 1-3,
The anchor coat layer laminated on the thin-walled body (A) is formed using at least one selected from the group consisting of urethane resins and polyester resins.
A face material characterized by that. In any one of Claims 1-4,
The pattern layer is laminated by a direct printing method,
A face material characterized by that. In claim 5,
The direct printing method is a printing method using a solvent-based ink,
A face material characterized by that. In any one of Claims 1-6,
On the other surface of the base material (B), a second thin body (C) made of a resin composition containing a rubber-reinforced resin is provided.
A face material characterized by that.   The face material according to any one of claims 1 to 7, which is used as a face material for building products, electrical products, vehicle products, furniture products, kitchen products and sundries products.   The face material according to any one of claims 1 to 8, which is used in a system kitchen.

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