JP5939825B2 - Resin article having silicon oxide film and method for producing the same - Google Patents

Description

  The present invention relates to a resin article formed with a silicon oxide film exhibiting excellent adhesion even after a high-temperature and high-humidity test, and more particularly to an extrusion or co-polymer having a specific copolycarbonate resin layer formed with a silicon oxide film. The present invention relates to an extruded polycarbonate resin sheet or film.

  Polycarbonate resin is widely used as a structural material to replace glass because of its excellent transparency, impact resistance, heat resistance, freedom of processing, lightness, etc., and is used in housings such as electrical, electronic, and OA equipment. It is widely used for automotive applications such as meter covers, liquid crystal display covers, window glass, sunroofs, instrument covers, and building materials such as daylighting roofing materials and window glass.

  When considering the use of a polycarbonate resin for the above applications, the polycarbonate resin has a problem that the surface hardness is low even when compared with other resins. In particular, in the case of a plastic product (molded product) having a transparent window portion or the like, the window portion or the like is required to have higher scratch resistance. In addition, a design such as a printed layer or a metal-like pattern having a predetermined pattern or character is appropriately required for other portions.

From the aspect of scratch resistance, a film or sheet with a hard coat having a high surface hardness exceeding 4H has been developed for the flat shape or gentle curved surface in the above-mentioned applications. It is used in a method of manufacturing an injection molded product by mounting it on
However, it cannot be used for an article having a curved surface that requires elongation. Therefore, such a highly scratch-resistant product depends on the method of coating this article after it is manufactured, but the operation is complicated and the product yield is low, and the thermoplastic resin has an extremely high degree of freedom in processing. It was something that could not be fully utilized.

  As this improvement, a method of forming an injection-molded product using a decorative film in which a thermocoatable hard coat layer is formed and appropriately designed on the back surface is disclosed (for example, Patent Document 1 = JP 2010-284910). The example of Patent Document 1 discloses a film in which a polyethylene terephthalate having a thickness of 125 μm is used as a base film, and a specific hard coat layer having a thickness of 4 μm is formed on one side. However, since the base film has been biaxially stretched and subjected to a heat setting step, it has been difficult to apply to thermoforming with a smaller R and a larger local elongation.

  In addition, from the aspect of the design such as a printing layer or metal-like design that has a predetermined pattern or characters required for other parts, development of printing ink that does not attack polycarbonate resin, ink resistance and higher durability Research and development has been conducted on surface treatment methods and primer layers for inorganic films that exhibit good adhesion, and further improvements are required.

JP 2010-284910 A

  As a result of intensive studies on the formation of an inorganic film of a polycarbonate resin sheet or film, the present inventors have found that a specific copolycarbonate resin can form a silicon oxide film with good adhesion after the initial and high-temperature and high-humidity tests. Based on this finding, the present invention has been completed.

That is, the present invention
(1) A resin article in which a SiO _y film (y is a positive number of 1 to 2) is formed on the surface of a resin layer, and the resin layer is represented by the following general formula (A) and general formula (B) And a layer containing a polycarbonate-polysiloxane copolymer (I) in which the proportion of the structural unit represented by the general formula (B) is 0.1 to 50% by weight. The resin article is characterized.
(R _{1 to} R ₁₀ in the general formulas (A) and (B) each independently represent hydrogen, halogen, or an alkyl group or aryl group which may have a substituent, and X represents —C (R ₁₁ ). (R ₁₂ )-, -S-, -S (= O) _2- , -C (= O)-, -O-, or-(CH ₂ ) a- (where R ₁₁ and R ₁₂ are Each independently represents hydrogen, halogen or an alkyl group or aryl group which may have a substituent, or R ₁₁ and R ₁₂ are bonded together to form a carbocyclic or heterocyclic ring; Represents the integer above.)

(2) The resin layer further includes a layer containing an aromatic polycarbonate resin, and a layer containing the copolymer (I) is provided on one or both sides of the layer containing the aromatic polycarbonate resin. A laminated body laminated by coextrusion molding, having a SiO _y film (y is a positive number of 1 to 2) on the surface of a layer containing at least one of the copolymers (I), and the copolymer ( It is a resin article as described in said (1) whose structural unit represented by general formula (B) in I) is 0.1 to 25 weight%.

(3) The resin layer further includes a layer containing an aromatic polycarbonate resin, and a layer containing the copolymer (I) is provided on one side of the layer containing the aromatic polycarbonate resin, A layered body having a total thickness of 70 to 1500 μm obtained by coextrusion molding a layer containing an acrylic resin having a thickness of 20 to 100 μm on the surface of the layer, and a SiO 2 layer on the surface of the layer containing the copolymer (I). _{The y} film (y is a positive number of 1 to 2), and the structural unit represented by the general formula (B) in the copolymer (I) is 0.1 wt% or more and 25 wt% or less, The resin article according to (1).
(4) The resin article according to (3), wherein the layer including the acrylic resin includes an ultraviolet absorber.
(5) The resin article according to the above (3) or (4), wherein the layer containing the acrylic resin has a thermoformable coating layer formed on the surface thereof.

(6) It has the structural unit represented by the said general formula (A) and general formula (B), and the ratio of the structural unit represented by general formula (B) is 0.1 to 50 weight%. Forming a resin layer having a layer containing a polycarbonate-polysiloxane copolymer (I);
Forming a SiO _y film (y is a positive number of 1 to 2) on the surface of the resin layer by a vacuum deposition method, a sputtering method, or a CVD method. It is.
(7) The method for producing a resin article according to (6), wherein the plasma treatment as a pretreatment is not performed when the SiO _y film (y is a positive number of 1 to 2) is formed.
(8) A laminate in which a layer containing an aromatic polycarbonate resin is formed and a layer containing the copolymer (I) is laminated on one or both sides of the layer containing the aromatic polycarbonate resin by coextrusion molding Forming the SiO _y film (y is a positive number of 1 to 2) on the surface of the layer containing at least one copolymer (I), and forming the copolymer (I ) In which the structural unit represented by the general formula (B) is 0.1% by weight or more and 25% by weight or less.
(9) A layer containing an aromatic polycarbonate resin is formed, a layer containing the copolymer (I) is formed on one surface of the layer containing the aromatic polycarbonate resin, and a thickness of 20 to 100 μm is formed on the other surface. wherein the surface of the layer comprising the step total thickness was laminated by the respective co-extrusion molding a layer containing an acrylic resin to form a stack of 70～1500Myuemu, and the copolymer (I) SiO _y film (y is 1 (A positive number of ˜2), and the structural unit represented by the general formula (B) in the copolymer (I) is 0.1 wt% or more and 25 wt% or less (the above) It is a manufacturing method of the resin article as described in 6) or (7).

SiO _y film (y is a positive number of 1 to 2) formed on the surface of the resin layer having a layer containing the polycarbonate-polysiloxane copolymer (I) in the present invention without performing pretreatment such as plasma treatment ) Shows good adhesion after the initial stage and after the high-temperature and high-humidity test, and enables production of a product with high added value.

First, the configuration of the present invention will be described.
Layer containing polycarbonate-polysiloxane copolymer (I) (PC-Si) The polycarbonate-polysiloxane copolymer (I) used in the present invention (hereinafter referred to as copolymer I as appropriate) has the following general formula. It is a copolymer I having a structural unit represented by (A) and the general formula (B) and having a proportion of the structural unit represented by the general formula (B) of 0.1 to 50% by weight. .
R _{1 to} R ₁₀ in the general formulas (A) and (B) each independently represent hydrogen, halogen, or an alkyl group or aryl group which may have a substituent. The halogen preferably includes fluorine, chlorine, bromine and iodine. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and sec-butyl. Furthermore, preferred examples of the aryl group include phenyl, benzyl, tolyl, o-xylyl and the like. Preferred examples of the substituent of the alkyl group or aryl group include halogen, methyl, ethyl and the like.
X in the general formula (A) is -C (R ₁₁ ) (R ₁₂ )-, -S-, -S (= O) _2- , -C (= O)-, -O-, or-( CH ₂₎ a- a show. Here, R ₁₁ and R ₁₂ each independently represent hydrogen, halogen or an alkyl group or aryl group which may have a substituent, or R ₁₁ and R ₁₂ are bonded together to form a carbocyclic or heterocyclic ring. Represents a group which forms The “halogen or optionally substituted alkyl group or aryl group” in R ₁₁ and R ₁₂ is the same as described above. Preferred examples of the carbocycle formed by combining R ₁₁ and R ₁₂ together include cyclopropane, cyclobutane, cyclohexane, and benzene. Preferred examples of the heterocyclic ring include pyridine and lactone. Said a represents an integer greater than or equal to 1, Preferably it is 1-6.

  This copolymer I is obtained by copolymerizing a dihydric phenol represented by the following general formula (1) and a polysiloxane represented by the general formula (2) with phosgene, carbonate, or chloroformate. It is done.

In the general formula (1), X and R _{1 to} R ₈ are the same as the substituents defined in the general formula (A). In the general formula (2), R ₉ and R ₁₀ are the same as the substituents defined in the general formula (B). Further, n represents an integer of 1 to 1000, Y represents _{halogen, -R 13 OH, -R 13 COOH} , -R 13 NH 2, -R 13 N (R 14) H or -SH,, R ₁₃ Represents a linear, branched or cyclic alkylidene group, an aryl-substituted alkylidene group, or an aryl group, R ₁₄ represents an alkyl, alkenyl, aryl, or aralkyl group, and m represents 0 or 1.
Preferred examples of the alkylidene group represented by R ₁₃ include vinylidene, benzylidene, and isopropylidene, and preferred examples of the aryl group include phenyl, benzyl, and o-xylyl. Preferred examples of the aryl-substituted alkylidene group represented by R ₁₃ include the above-mentioned alkylidene groups substituted with the above-mentioned aryl group.
Preferred examples of the alkyl represented by R ₁₄ include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, sec-butyl and the like, and examples of alkenyl include vinyl, 2-propenyl and the like. Preferred examples of the aryl include phenyl, benzyl, o-xylyl and the like, and preferred examples of the aralkyl group include 2-phenylethyl, methylphenyl and the like.

In the present invention, when the copolymer I is used as a monolayer film, a polycarbonate-polysiloxane in which the proportion of the structural unit represented by the general formula (B) is 0.1 to 50% by weight, particularly 1 to 30% by weight. A copolymer is preferred. If the proportion of the structural unit represented by the general formula (B) exceeds 50% by weight, it may be difficult to produce a film, and if it is less than 0.1% by weight, surface characteristics may not be exhibited.
In the present invention, when the copolymer I is used for co-extrusion, the proportion of the structural unit represented by the general formula (B) is from 0.1% by weight to 25% by weight, particularly from 0.1 to 20% by weight. Polysiloxane copolymers are preferred. When the proportion of the structural unit represented by the general formula (B) exceeds 25% by weight, the interlayer adhesion with the aromatic polycarbonate resin becomes insufficient, and the transparency is lowered and the design property is deteriorated. If it is less than%, improvement in the adhesion of the silicon oxide film will be insufficient.
The viscosity average molecular weight of the copolymer I is preferably 15,000 to 100,000, more preferably 20,000 to 50,000. When the viscosity average molecular weight is smaller than 15,000, the film strength is not sufficient, and when it exceeds 100,000, the productivity tends to decrease.

Examples of the dihydric phenol represented by the general formula (1) used for the production of the copolymer I include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, Bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ) Propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2,2-bis (4-hydroxy -3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-Hide Loxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) ) Diphenylmethane and the like are preferably exemplified. Among these, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are preferable.
In addition, examples of the polysiloxane represented by the general formula (2) preferably include compounds represented by the following general formulas (3) to (9).

In the general formulas (3) to (9), R ₉ , R ₁₀ , R ₁₄ and n are the same as those defined in the general formula (2). b represents a positive integer, preferably 1-5. Among these, α, ω-bis (3- (o-hydroxyphenyl) propyl) polydimethylsiloxane is particularly preferable.
In addition, those having hydroxyphenyl groups at both ends (dihydric phenol) are phenols having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, allylphenol, or isopropenylphenol with a predetermined polymerization degree. It is easily produced by hydrosilation reaction at the end of a polysiloxane chain having n.

  Usually, a terminal stopper or a molecular weight modifier is used in the production of a polycarbonate resin. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, tribromophenol, etc., long-chain alkylphenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid And hydroxybenzoic acid alkyl ester, hydroxyphenyl alkyl acid ester, alkyl ether phenol and the like. The amount of use is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, with respect to 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination.

  Further, a branching agent can be used in combination in the range of 0.01 to 3 mol%, particularly 0.1 to 1.0 mol%, with respect to the dihydric phenol compound, to form a branched polycarbonate. Glycine, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 1, 3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α , α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like, and 3,3-bis (4-hydroxyaryl) oxindole (= isa) Chin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. It is exemplified.

  Although the thickness of the layer containing the copolymer I can be appropriately selected depending on the application of the resin article, it is preferably 5 to 500 μm, more preferably 10 to 300 μm. When the thickness of the layer containing the copolymer I is less than 5 μm, lamination becomes difficult, and when it exceeds 500 μm, the flexibility of the film may be impaired.

Layer containing aromatic polycarbonate resin (BPA-PC) The aromatic polycarbonate resin used in a preferred embodiment of the present invention is represented by the general formula (1) used for the above-mentioned polycarbonate-polysiloxane copolymer (I). It is produced by interfacial polymerization using a monohydric phenol or a small amount thereof and a small amount of a polyhydroxy compound and phosgene, or is produced by a transesterification reaction between the above aromatic dihydroxy compound and a diester of carbonic acid. A good thermoplastic polycarbonate polymer.
The aromatic polycarbonate resin used in the preferred embodiment of the present invention is preferably one capable of producing a sheet by ordinary extrusion molding, and the viscosity average molecular weight is 15,000 to 40,000, preferably 20,000 to 35, 000, more preferably 22,500 to 25,000.

  The aromatic polycarbonate resin used in the preferred embodiment of the present invention can be blended with various additives used in conventional polycarbonate resins as desired, including reinforcing materials, fillers, stabilizers, ultraviolet rays. Examples include absorbents, antistatic agents, lubricants, mold release agents, dyes, pigments, other flame retardants, and elastomers for improving impact resistance.

Layer containing acrylic resin The acrylic resin used in a preferred embodiment of the present invention is preferably a copolymer of methyl methacrylate and an acrylate such as methyl acrylate or ethyl acrylate, and the copolymer composition and molecular weight can be appropriately selected according to the co-extrusion conditions. The copolymer composition ratio is preferably 80 to 99.5% methyl methacrylate and 0.5 to 20% acrylate such as methyl or ethyl acrylate.
Moreover, the acrylic resin containing a crosslinking component can be used in the range which can be extrusion-molded and does not impair transparency. The molecular weight is 3 to 300,000 in terms of weight average molecular weight, but is not limited thereto. As the load deflection temperature of the acrylic resin is higher, the glass transition temperature is higher, the roll transfer temperature is closer to the roll transfer temperature of the polycarbonate resin, and a laminate having excellent roll transfer properties and excellent appearance can be obtained. Therefore, the load deflection temperature of the acrylic resin is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, and particularly preferably 100 ° C. or higher. In order to ensure high pencil hardness, it is preferable that the acrylic resin contains substantially no rubber component.

  The acrylic resin production method is generally roughly classified into an emulsion polymerization method, a suspension polymerization method, and a continuous polymerization method. The acrylic resin used in the preferred embodiment of the present invention was produced by any polymerization method. A resin can also be used, but it is preferably produced by a suspension polymerization method or a continuous polymerization method, and more preferably produced by a continuous polymerization method. The continuous production method is divided into a continuous bulk polymerization method and a continuous solution polymerization method. In the present invention, an acrylic resin obtained by either production method can be used.

  In the acrylic resin, it is preferable to add a known ultraviolet absorber in an amount of 0.005 to 3.0% by weight with respect to the acrylic resin for the purpose of maintaining the weather resistance for a long period of time. In order to prevent thermal deterioration of the acrylic resin during coextrusion molding, a known antioxidant and anti-coloring agent may be added. The antioxidant is preferably added in an amount of 0.01 to 3% by weight based on the acrylic resin. The coloring inhibitor can be added in an amount of 0.01 to 3% by weight based on the acrylic resin. When the total amount of the ultraviolet absorber, antioxidant and anti-coloring agent is less than 0.1% by weight based on the acrylic resin, sufficient weather resistance is not exhibited. Moreover, even if it is added in excess of 5% by weight, not only a further improvement in weather resistance can be expected, but these additives may cause bleed-out, causing whitening, and reducing adhesion and impact strength. is there.

  Examples of the ultraviolet absorber added to these acrylic resins include benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, and triazine-based ultraviolet absorbers. Examples of the benzotriazole ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzo Triazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl) -6- (2H-benzotriazole -2-yl) phenol] and the like, and as the benzophenone-based ultraviolet absorber, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4 ′ -Chlorbenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2,2-dihydroxy Ci-4,4'-dimethoxybenzophenone and the like can be exemplified.

  Examples of the salicylic acid phenyl ester ultraviolet absorber include pt-butylphenyl salicylic acid ester, and the triazine ultraviolet absorber includes 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl). ) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-) 4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3 5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) ) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy) -4-butoxyethoxy) -1,3,5-triazine and the like can be mentioned, but are not limited to these, and generally available ultraviolet absorbers and the like are included.

  Although the thickness of the layer containing an acrylic resin can be suitably selected according to the use of the resin article, it is preferably 20 to 100 μm, and more preferably 30 to 80 μm. If the thickness of the layer containing the acrylic resin is less than 20 μm, the desired surface hardness may not be obtained, and if it exceeds 100 μm, the impact resistance may be insufficient.

Production of Film or Sheet Using the above-described resin, a film or sheet as an example of the resin article of the present invention is usually produced by extrusion or coextrusion molding.
Examples of the extrusion molding method include T-die film molding, inflation film molding, and calendar molding. When the copolymer I is discharged from the die by extrusion, the shear rate is preferably 2.0 to 80.0 (1 / sec). This is to obtain the required fluidity and facilitate extrusion.
In the present invention, a resin layer having only a layer containing the copolymer I may be formed, but a layer containing an aromatic polycarbonate resin is formed, and one or both surfaces of the layer containing the aromatic polycarbonate resin are formed. It is also preferable to form a laminate in which layers containing the copolymer I are laminated by coextrusion molding.
In addition, a layer containing an aromatic polycarbonate resin is formed, a layer containing the copolymer I is included on one surface of the layer including the aromatic polycarbonate resin, and an acrylic resin having a thickness of 20 to 100 μm is included on the other surface. It is also preferable to form a laminate having a total thickness of 70 to 1500 μm obtained by laminating layers by coextrusion.

  The total thickness of the extruded and coextruded film is preferably 70 to 1500 μm. When the thickness is less than 70 μm, it is difficult to produce a film, and when it exceeds 1500 μm, the flexibility as a film is lowered.

As described above, in the present invention, a sheet-like or film-like laminate having a layer containing the copolymer I can be produced by coextrusion on one or both sides of the layer containing the aromatic polycarbonate resin, A sheet-like or film-like laminate having a layer containing the copolymer I on one side of the layer containing the aromatic polycarbonate resin and a layer containing the acrylic resin on the other side can be produced by coextrusion.
Co-extrusion is constituted by one main extruder for extruding an aromatic polycarbonate resin and a sub-extruder for extruding the copolymer I or acrylic resin constituting the coating layer.
The temperature condition of the main extruder is usually 230 to 290 ° C, preferably 240 to 280 ° C, and the temperature condition of the sub-extruder is usually 220 to 270 ° C, preferably 230 to 260 ° C. In order to remove foreign substances in the resin, it is preferable to install a polymer filter on the upstream side of the die of the extruder.

  The molten resin can be produced using a known method such as a multi-manifold method or a feed block method. In the case of a multi-manifold die, the molten resin laminated in the die is molded into a sheet inside the die, and then guided to a molding roll (polishing roll) whose surface is mirror-finished. Mirror finish and cooling are performed to form a laminate. Moreover, the molten resin laminated | stacked with the feed block is guide | induced to sheet | seat shaping | molding dies, such as T-die, and after shape | molding in a sheet form, surface finishing and cooling are performed with a shaping | molding roll, and a laminated body is formed. The die temperature is usually 250 to 320 ° C, preferably 270 to 300 ° C, and the forming roll temperature is usually 100 to 200 ° C, preferably 110 to 190 ° C. As the roll, a vertical roll or a horizontal roll can be appropriately used.

On the surface of the layer containing the copolymer I in a film or sheet produced from a resin article formed with a silicon oxide film or more, a silicon oxide thin film (ie, SiO 2) is formed by vacuum deposition, sputtering, or CVD. _y film (y is a positive number of 1 to 2)) is formed to obtain the resin article of the present invention. Each method is publicly known, but will be briefly described below.
The vacuum evaporation method is one of methods for forming a surface treatment or a thin film in which a metal, an oxide, or the like is evaporated and adhered to the surface of a material. In other words, in a vacuumed container, the vapor deposition material is heated by resistance heating, electron beam, high frequency induction, laser, etc., and evaporated or sublimated to adhere to a film placed at a remote location to form a thin film It is a method of doing.
Sputtering is a method in which a metal to be deposited as a thin film in a vacuum chamber is set as a target, a rare gas element or nitrogen that is ionized by applying a high voltage is collided, and atoms on the target surface are blown off to the substrate. This is a method of forming a thin film.
In either film forming method, when a silicon oxide film is generally formed on plastic, it is common to improve the adhesion by performing a pretreatment such as plasma treatment or Ar ion gun. . However, in the present invention, a sufficiently adherent silicon oxide film can be obtained without such pretreatment, which is different from the conventional method.

  The thickness of the silicon oxide film is preferably 1 to 100 nm. More preferably, it is 1-50 nm. In addition, this oxide film is suitably used as another inorganic film, for example, a multilayered antireflection film, a metal-like film for design, and other primer films for adhesion.

In the present invention, when a layer containing an acrylic resin is provided on one side of a layer containing an aromatic polycarbonate resin, a thermoformable coating film, typically a hard coat, is formed on the layer containing the acrylic resin. By forming a film having such a function, a hard coat is formed on a curved surface, and a decorative film having a design pattern such as a metal is formed on the opposite surface.
The thermoformable hard coat film is formed by applying a paint that can be followed during thermoforming. Of course, existing paints can also be applied as paints, but those in which some components such as solvent components are devised for the laminate are preferred.

  Further, a multilayer resin article in which a metal-like film for design is formed on the silicon oxide film on one side of the present invention, and a coating film that can be appropriately thermoformed on the opposite side is formed by thermoforming gold. After being mounted on a mold or thermoformed in a mold, a transparent thermoplastic resin is injection molded to obtain a molded product. At this time, the silicon oxide film is firmly bonded, and suppresses the occurrence of defects such as peeling of the injection molding resin due to peeling from this layer.

Hereinafter, the present invention will be described by way of examples. The present invention is not limited by these examples.
In Examples and Comparative Examples, the following polycarbonate resins, acrylic resins, ultraviolet absorbers, antioxidants, and anti-coloring agents were used.
1. BPA-PC: Bisphenol A polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon S-1000, viscosity average molecular weight 25,000.
2. PC-Si: Polycarbonate-polysiloxane copolymer Polycarbonate-polysiloxane copolymer produced in Production Examples 1 to 3 below.
3. PMMA: Acrylic resin The acrylic resin produced in Production Example 4 below.
4). Additive for acrylic resin:
The following were used for the acrylic resin lubricant, ultraviolet absorber, antioxidant, and coloring inhibitor.
Lubricant: Stearyl alcohol, manufactured by Kishida Chemical Co., Ltd.
UV absorber: 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine (manufactured by Ciba Specialty Chemicals, trade name: Tinuvin 1577).
Antioxidant: 2,6-di-t-butyl-4-methylphenol (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer BHT).
Anti-coloring agent: Asahi Denka Kogyo Co., Ltd., trade name: PEP36.

The measurement and evaluation of various physical properties in Examples and Comparative Examples were performed by the following methods.
1. Adhesion test: Adhesion was measured in accordance with JIS 5600-5-4.
2. High temperature and high humidity test: After holding for 96 hours in an environment of 85 ° C. and 85%, the adhesion was measured according to JIS 5600-5-4.

Production Example 1 (PC-Si-I)
In 580 liters of 8.8% (W / V) aqueous sodium hydroxide solution, 91.2 kg of bisphenol A (BPA) and polysiloxane represented by the above general formula (3) (R ₉ and R ₁₀ are each a methyl group, n = 41, b = 3 and ortho bond) 5.95 kg and hydrosulfite 100 g were added and dissolved. To this, 360 liters of methylene chloride was added, and 1.44 kg of pt-butylphenol (PTBP) was added while stirring at 15 ° C., and then 53.0 kg of phosgene was blown in over 60 minutes. After the blowing, the reaction liquid was emulsified by vigorous stirring. After emulsification, 100 ml of triethylamine was added, and the mixture was stirred for about 1 hour for polymerization. The polymerization solution was separated into an aqueous layer and an organic layer, the organic layer was neutralized with sulfuric acid, and washing was repeated until the pH of the washing solution became neutral. Then, 470 liters of isopropanol was added to precipitate the polymer. The precipitate was filtered and dried to obtain a white powdery polycarbonate-polysiloxane copolymer (PC-Si) resin. The proportion of the structural unit represented by the general formula (A) in the obtained polycarbonate-polysiloxane copolymer is about 95% by weight, and the proportion of the structural unit represented by the general formula (B) is about 5% by weight. It is.

Production Example 2 (PC-Si-II)
The same method as in Production Example 1 was used except that the constituent unit of the polysiloxane copolymer was changed to 20% by weight. The proportion of the structural unit represented by the general formula (A) in the obtained polycarbonate-polysiloxane copolymer is about 80% by weight, and the proportion of the structural unit represented by the general formula (B) is about 20% by weight. It is.

Production Example 3 (PC-Si-III)
The same method as in Production Example 1 was used except that the constituent unit of the polysiloxane copolymer was changed to 50% by weight. The proportion of the structural unit represented by the general formula (A) in the obtained polycarbonate-polysiloxane copolymer is about 50% by weight, and the proportion of the structural unit represented by the general formula (B) is about 50% by weight. It is.

Production Example 4 (PMMA: according to the method described in JP-A-7-133303)
88 parts by weight of methyl methacrylate, 4 parts by weight of methyl acrylate, 8 parts by weight of methanol, 0.032 parts by weight of di-t-butyl peroxide (2 × 10 ⁻³ mol / L) and 0.21 parts by weight of n-dodecyl mercaptan ( 10 × 10 ⁻³ mol / L) was mixed, and dissolved oxygen was removed by blowing nitrogen to prepare a raw material solution.
5 kg of the raw material liquid was added in advance to a 6 L internal polymerization tank equipped with a jacket for circulating the heat medium and a helical ribbon stirring blade, sealed and heated to 150 ° C. with sufficient stirring and uniform mixing. The polymerization was continued until the monomer conversion reached 75% and the polymer concentration reached 69%, and then this raw material solution was continuously supplied to the polymerization tank at a rate of 1 kg / h.

When the polymerization temperature was maintained at 150 ° C. and the average residence time was maintained at about 5 hours, the viscosity of the polymerization solution was maintained at 45 Pa · sec, the monomer conversion was 75%, and the polymer concentration was 69%. The polymer solution was extracted at a flow rate of 1 kg / h, heated to 250 ° C., and flushed into a devolatilization tank under reduced pressure. 100 parts by weight of the devolatilized polymer was blended with 0.2 parts by weight of the lubricant, 1.0 part by weight of the UV absorber, 0.1 part by weight of the antioxidant, and 0.1 part by weight of the anti-coloring agent. After kneading, under pressure, it is extracted in a molten state from the bottom of a devolatilization tank equipped with a polymer filter having a leaf disk made of SUS-316L with an absolute filtration accuracy of 10 μm, taken out into a strand form with a die, pelletized with a pelletizer after water cooling did.
The obtained pellets were 0.27% by weight methyl methacrylate and 0.01% by weight methyl acrylate as residual volatile components, and n-dodecyl mercaptan as a polymerization initiator and a chain transfer agent was not observed by GC analysis. The external appearance of the obtained acrylic resin (PMMA) was colorless and transparent, the weight average molecular weight (Mw) was 85,000, and the heat distortion temperature was 105 degreeC from GPC measurement.

Example 1
As an aromatic polycarbonate resin extruder (main extruder), a barrel diameter of 65 mm and a screw L / D = 35 were used, and the cylinder temperature was set to 270 ° C. Moreover, the extruder (sub-extruder) of polycarbonate-polysiloxane copolymer resin which forms a coating layer was set to a cylinder temperature of 260 ° C. using a barrel diameter of 32 mm and a screw L / D = 32.
When two types of resins are melt-extruded at the same time and laminated, a feed block is used, and PC-Si-I (polycarbonate) obtained in Production Example 1 is formed on one side of a layer containing BPA-PC (bisphenol A polycarbonate resin). -A layer containing a polysiloxane copolymer) was laminated.

The die head temperature is 260 ° C., and the resin laminated and integrated in the die is a mirror-finished horizontal polishing roll having three polishing rolls (No. 1 roll temperature 130 ° C., No. 2 roll temperature 130 ° C., No. 3 roll temperature Set to 185 ° C.). A bank was formed at the first inflow roll interval, and then the second and third rolls were passed through to extrude a 300 μm thick coextruded sheet.
At this time, the rotation speed of the main extruder and the sub-extruder was set so that the discharge amount ratio was main / sub = 270/30 to obtain a polycarbonate resin laminate. The evaluation results of the manufactured laminate are shown in Table 1. In addition, the thickness of the layer containing PC-Si-I (polycarbonate-polysiloxane copolymer) in the 300 μm-thick coextruded sheet was 30 μm.
The thin film substance was evaporated with an electron gun under reduced pressure of 10 ⁻³ to 10 ⁻⁴ Pa using the CES-350 type vapor deposition apparatus manufactured by SYNCHRON Co., Ltd. with respect to the obtained polycarbonate resin laminate. As the thin film material, a polycarbonate resin laminate was obtained in which silicon dioxide thin films were laminated from the PC-Si layer side so as to have a thickness of 50 nm. The evaluation results of the manufactured laminate are shown in Table 1.

(Example 2)
In Example 1, a polycarbonate resin laminate was obtained in the same manner except that the rotational speeds of the main extruder and the sub-extruder were set so that the discharge amount ratio was main / sub = 290/10.
The evaluation results of the manufactured laminate are shown in Table 1. In addition, the thickness of the layer containing PC-Si-I (polycarbonate-polysiloxane copolymer) in the 300 μm-thick coextruded sheet was 10 μm.
Further, in the same manner as in Example 1, a polycarbonate resin laminate in which silicon dioxide thin films were laminated to a thickness of 50 nm was obtained. The evaluation results of the manufactured laminate are shown in Table 1.

(Example 3)
A coextruded sheet was prepared by laminating a layer containing PMMA on one side of a layer containing an aromatic polycarbonate resin and a layer containing PC-Si-I (polycarbonate-polysiloxane copolymer) on the other side.
Two main extruders similar to Example 1 and two sub-extruders similar to Example 1 were used, and the number of revolutions of the main extruder and the two sub-extruders was such that the discharge amount ratio was main / sub / sub = 240 / Same as Example 1 except that the setting is 30/30 and the polishing roll conditions are set to (No. 1 roll temperature 110 ° C., No. 2 roll temperature 130 ° C., No. 3 roll temperature 185 ° C.) It was.
When three types of resins are melt-extruded and laminated at the same time, a feed block is used, and the layer containing PMMA obtained in Production Example 4 is used on one side of the layer containing BPA-PC (bisphenol A polycarbonate resin). A layer containing PC-Si-I (polycarbonate-polysiloxane copolymer) obtained in Production Example 1 was laminated on the opposite surface. Further, in the same manner as in Example 1, a polycarbonate resin laminate in which a silicon dioxide thin film was laminated on a layer containing PC-Si so as to have a thickness of 50 nm was obtained. The evaluation results of the manufactured laminate are shown in Table 1.

Example 4
In Example 3, the total thickness was 1000 μm, and the rotation speeds of the main extruder and the two sub-extruders were set except that the discharge amount ratio was main / sub / sub = 930/60/10. A polycarbonate resin laminate was produced in the same manner as in Example 3. The evaluation results of the manufactured laminate are shown in Table 1.

(Example 5)
In Example 1, using only the main extruder, PC-Si-I (polycarbonate-polysiloxane copolymer) was extruded at a cylinder temperature of 260 ° C. to produce a sheet of PC-Si alone. The evaluation results are shown in Table 1.

(Example 6)
The same procedure as in Example 1 was performed except that PC-Si (polycarbonate-polysiloxane copolymer) was replaced with that prepared in Production Example 2. The evaluation results are shown in Table 1.

(Example 7)
The same procedure as in Example 2 was performed except that PC-Si (polycarbonate-polysiloxane copolymer) was replaced with that produced in Production Example 2. The evaluation results are shown in Table 1.

(Example 8)
The same procedure as in Example 3 was performed except that PC-Si (polycarbonate-polysiloxane copolymer) was replaced with that prepared in Production Example 2. The evaluation results are shown in Table 1.

Example 9
The same procedure as in Example 4 was performed except that PC-Si (polycarbonate-polysiloxane copolymer) was replaced with that prepared in Production Example 2. The evaluation results are shown in Table 1.

(Example 10)
The same procedure as in Example 5 was performed except that PC-Si (polycarbonate-polysiloxane copolymer) was replaced with that prepared in Production Example 2. The evaluation results are shown in Table 1.

(Example 11)
The same operation as in Example 5 was carried out except that PC-Si (polycarbonate-polysiloxane copolymer) was replaced with that produced in Production Example 3. The evaluation results are shown in Table 1.

(Comparative Example 1)
In Example 1, using only the main extruder, BPA-PC (bisphenol A polycarbonate resin) was extruded at a cylinder temperature of 2700C to produce a sheet of BPA-PC alone. The evaluation results are shown in Table 1.

(Comparative Example 2)
In Example 3, the sub-extruder for the layer containing PC-Si (polycarbonate-polysiloxane copolymer) was not used, and the number of revolutions of the main extruder and the sub-extruder was such that the discharge amount ratio was main / sub = 270. A polycarbonate resin laminate was produced in the same manner as in Example 3 except that the setting was / 30. A thin film of silicon dioxide was formed and evaluated on the layer containing the PMMA of the manufactured laminate. The evaluation results are shown in Table 1.

  As is clear from Table 1, the sheet of the present invention having a layer containing PC-Si (polycarbonate-polysiloxane copolymer) is excellent not only in the initial adhesion but also in the adhesion after the high-temperature and high-humidity test. You can see that

Claims (7)

A resin article in which a SiO _y film (y is a positive number of 1 to 2) is formed on the surface of a resin layer, wherein the resin layer is represented by the following general formula (A) and general formula (B) has units, and the general formula polycarbonate amount of the structural units is 25% by weight 0.1 represented by (B) - have a layer containing a polysiloxane copolymer (I),
(R _{1 to} R ₁₀ in the general formulas (A) and (B) each independently represent hydrogen, halogen, or an optionally substituted alkyl group or aryl group, and X represents —C (R ₁₁ ) (R ₁₂ )-, -S-, -S (= O) _2- , -C (= O)-, -O-, or-(CH ₂ ) a- (where R ₁₁ and R ₁₂ are Each independently represents hydrogen, halogen or an optionally substituted alkyl group or aryl group, or R ₁₁ and R ₁₂ are bonded together to form a carbocyclic or heterocyclic ring; Represents an integer of 1 or more.)
The resin layer further includes a layer containing an aromatic polycarbonate resin, and a layer containing the copolymer (I) is coextruded on one or both sides of the layer containing the aromatic polycarbonate resin. The resin article having a SiO _y film (y is a positive number of 1 to 2) on the surface of the layer containing at least one copolymer (I) . The resin layer has a total thickness obtained by laminating a resin layer made of the copolymer (I) on one side of the aromatic polycarbonate resin layer and an acrylic resin layer having a thickness of 20 to 100 μm on the other side by coextrusion molding. A polycarbonate resin laminate having a thickness of 70 to 1500 μm, having a SiO _y film (y is a positive number of 1 to 2) on the surface of the resin layer of the copolymer (I), and the copolymer (I) The resin article having a silicon oxide film according to claim 1, wherein the structural unit represented by the general formula (B) is 0.1 wt% or more and 25 wt% or less. The resin article according to claim 2 , wherein the layer containing the acrylic resin contains an ultraviolet absorber. The resin article according to claim 2 or 3 , wherein the layer containing the acrylic resin is formed by forming a thermoformable coating layer on the surface thereof. Polycarbonate-polypropylene having structural units represented by the following general formula (A) and general formula (B), and the proportion of the structural units represented by the general formula (B) is 0.1 to 25 % by weight Forming a resin layer having a layer containing the siloxane copolymer (I);
Forming a layer containing an aromatic polycarbonate resin and forming a laminate in which a layer containing the copolymer (I) is laminated on one or both sides of the layer containing the aromatic polycarbonate resin by coextrusion molding When,
Forming a SiO _y film (y is a positive number of 1 to 2) on the surface of the layer containing at least one copolymer (I) by vacuum deposition, sputtering, or CVD;
The manufacturing method of the resin article characterized by having.
(R _{1 to} R ₁₀ in the general formulas (A) and (B) each independently represent hydrogen, halogen, or an optionally substituted alkyl group or aryl group, and X represents —C (R ₁₁ ) (R ₁₂ )-, -S-, -S (= O) _2- , -C (= O)-, -O-, or-(CH ₂ ) a- (where R ₁₁ and R ₁₂ are Each independently represents hydrogen, halogen or an optionally substituted alkyl group or aryl group, or R ₁₁ and R ₁₂ are bonded together to form a carbocyclic or heterocyclic ring; Represents an integer of 1 or more.) The method for producing a resin article according to claim 5 , wherein a plasma treatment that is a pretreatment is not performed when forming the SiO _y film (y is a positive number of 1 to 2). A layer containing an aromatic polycarbonate resin is formed, a layer containing the copolymer (I) is formed on one surface of the layer containing the aromatic polycarbonate resin, and an acrylic resin having a thickness of 20 to 100 μm is formed on the other surface. A step of forming a laminate having a total thickness of 70 to 1500 μm by laminating layers including coextrusion, and the SiO _y film (y is 1 to 2) on the surface of the layer containing the copolymer (I). A step of forming a positive number)
The manufacturing method of the resin article of Claim 5 or 6 whose structural unit represented by general formula (B) in the said copolymer (I) is 0.1 to 25 weight%.