JP2010173195A - Polycarbonate resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin laminate, which has a good appearance and is excellent in abrasion resistance and scratch resistance. <P>SOLUTION: The laminate is formed by laminating a polycarbonate resin substrate 10, a first layer comprising a composition containing a hydrolyzable silicon compound derivative and glass fiber, and a second layer comprising silica formed by the atmospheric-pressure glow plasma method 101 in this order. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin laminate that can be suitably used for, for example, window materials or sunroofs of various vehicles, various building material sheets, display face plates, and the like.

Attempts have been made to use transparent plastic materials as substitutes for glass by taking advantage of its impact resistance, light weight, ease of processing, etc., especially for the purpose of preventing scattering of fragments at the time of collision, etc. It is desired to apply these to window materials for automobiles.
As such a transparent plastic material, the use of a polycarbonate resin has been particularly studied. However, the polycarbonate resin has a lower surface hardness than glass, and has problems in terms of wear resistance, scratch resistance, and the like. It was.

  Therefore, in order to improve the surface hardness, abrasion resistance, scratch resistance, etc. of the polycarbonate resin, etc., an inorganic oxide layer is formed on the polycarbonate resin surface by vacuum vapor deposition, chemical vapor deposition (CVD), or the like. A method of laminating the layers has been proposed. Specifically, for example, Patent Document 1 proposes a method of forming a silica film by electron beam heating. Patent Document 2 proposes a method in which a layer of a cured organosiloxane containing colloidal silica is formed on the surface of a polycarbonate resin, and a silica film is laminated on the cured product layer by a sputtering method.

  Furthermore, a method of coating an acrylic resin layer on a polycarbonate resin surface and further coating a silica film thereon by a wet method has been proposed (Patent Documents 3 to 5).

JP 2004-175094 A JP 2004-237513 A Japanese Unexamined Patent Publication No. Sho 63-27879 Japanese Patent Laid-Open No. 01-306476 JP 2000-318106 A

  However, when an inorganic oxide layer is formed directly on a polycarbonate resin substrate by a vacuum vapor deposition method or a CVD method, cracks are likely to occur due to the difference in thermal expansion coefficient between the polycarbonate resin substrate and the inorganic oxide. In addition, since the adhesive force at the interface between the polycarbonate resin substrate and the inorganic oxide layer is insufficient, a poor performance due to deterioration with time, etc. is observed, and a polycarbonate resin laminate having sufficient performance can be obtained. It was difficult.

  In the method of laminating a silica film by electron beam heating as described in Patent Document 1 or the method of laminating a silica film by a sputtering method as described in Patent Document 2, lamination of the silica film In this case, an expensive vacuum apparatus is required, and as described in Patent Document 2, it takes a long time at high temperature to cure the mixture of colloidal silica and alkoxysilane hydrolyzate. There was a problem such as that would occur.

  Furthermore, the silica film coated by a wet method as described in Patent Documents 3 to 5 has a problem that the hardness of the silica film is low and the wear resistance and scratch resistance are not sufficient.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate resin laminate having a good appearance and excellent wear resistance and scratch resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor formed a first layer comprising a composition containing a hydrolyzable silicon compound derivative and glass fiber on a polycarbonate resin substrate, and then on the first layer. In addition, it was found that by forming a silica layer by an atmospheric pressure glow plasma method, a polycarbonate resin laminate having excellent wear resistance and scratch resistance can be obtained, and the present invention has been reached.

  That is, the gist of the present invention is a polycarbonate resin substrate, a first layer made of a composition containing a hydrolyzable silicon compound derivative and glass fiber, and a second layer made of silica formed by an atmospheric pressure glow plasma method. Are laminated in this order in a polycarbonate resin laminate.

Under the present circumstances, it is preferable that content of the glass fiber in the said composition is 0.05 weight% or more and 5 weight% or less.
The hydrolyzable silicon compound derivative is preferably a hydrolyzate of tetraethoxysilane.
Furthermore, it is preferable that the carbon amount measured by the X-ray photoelectron spectroscopy (XPS) method on the surface of the second layer is 5 atm% or less.
The second layer is preferably formed using dimethyldiethoxysilane.
Furthermore, a primer layer containing a thermoplastic resin and / or a curable resin may be provided between the polycarbonate resin substrate and the first layer.

The polycarbonate resin laminate of the present invention is a layer comprising a composition containing a hydrolyzable silicon compound derivative and glass fiber between a polycarbonate resin substrate and a silica layer (second layer) formed by an atmospheric pressure plasma method. Since the (first layer) is present, cracks hardly occur and the wear resistance and scratch resistance are excellent. In addition, since the first layer can relieve stress that causes cracks when the second layer is formed, an excellent polycarbonate resin laminate in which cracks are unlikely to occur can be obtained.
Therefore, the polycarbonate resin laminate of the present invention can have good appearance, high surface hardness, and excellent wear resistance and scratch resistance.

Moreover, since the glass fiber used for the first layer is industrially easily available and can be procured at a low cost, it can be said that the polycarbonate resin laminate of the present invention is highly practical in terms of cost.
Furthermore, the polycarbonate resin laminate of the present invention has an advantage that it can be produced without requiring an expensive vacuum device or the like.

It is a schematic sectional drawing which shows an example of an atmospheric pressure glow plasma generator which can be used for formation of the 2nd layer in the polycarbonate resin laminated body of this invention.

  Hereinafter, the present invention will be described in detail with reference to embodiments, examples, etc., but the present invention is not limited to the following embodiments, examples, etc., and can be arbitrarily set within the scope of the present invention. Can be changed and implemented.

[1. Overview]
The polycarbonate resin laminate of the present invention comprises a polycarbonate resin substrate, a first layer comprising a composition containing a hydrolyzable silicon compound derivative and glass fiber, and a second layer comprising silica formed by an atmospheric pressure glow plasma method. Are laminated in this order, as long as the effects and objects of the present invention are not impaired, the layer structure and the like are not particularly limited. For example, between the polycarbonate resin substrate and the first layer, An arbitrary layer such as a primer layer may be formed between the first layer and the second layer, and an arbitrary layer is formed under the polycarbonate resin substrate or on the second layer. Also good.

[2. Physical properties of polycarbonate resin laminate]
The light transmittance of the polycarbonate resin laminate of the present invention is preferably 5% or more, more preferably 10% or more, and particularly preferably 20% or more. The upper limit of the light transmittance is preferably 95% or less, more preferably 90% or less, and particularly preferably 85% or less. By setting the light transmittance to the above range, a polycarbonate resin laminate used for various applications as described later can be obtained. The light transmittance is a value measured for light having a wavelength of 500 nm with a UV-spectrophotometer (V-650 manufactured by JASCO).

The abrasion resistance of the polycarbonate resin laminate of the present invention can be evaluated by the light transmittance retention after the abrasion resistance test measured by the following method. The light transmittance retention after the abrasion resistance test is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more. By setting it as the above-mentioned value or more, it can be set as the polycarbonate resin laminated body with high abrasion resistance used for the various uses which are mentioned later.
The light transmittance retention after the abrasion resistance test is that the polycarbonate resin laminate is worn 100 times with a steel wool abrasion tester (Lens coating strength tester kit manufactured by Autex Co., Ltd.) with a load of 1 kg. The value obtained by dividing the difference between the initial light transmittance (before the test) and the light transmittance after the abrasion resistance test by the initial light transmittance at the time of the test is 100% converted. Here, the light transmittance is measured by the method described above.

The Martens hardness of the polycarbonate resin laminate of the present invention is preferably 200 Nmm ^-2 or more, more preferably 400 Nmm ^-2 or more, and particularly preferably 450 Nmm ^-2 or more. By setting it to the above lower limit value or more, it is possible to obtain a high-hardness polycarbonate resin laminate applicable to various uses. In the polycarbonate resin laminate of the present invention, the surface hardness of the second layer can be increased due to the presence of the first layer having a high hardness composed of the hydrolyzable silicon compound derivative and the glass fiber. Presumed. And since this 1st layer can relieve | moderate the stress which causes the crack which arises in the case of 2nd layer formation, it is thought that the silica layer which a crack does not produce easily is obtained.
Martens hardness is measured with an ultra-micro hardness meter (DUH-211 manufactured by Shimadzu Corporation), and refers to a measured value when the indentation depth is 1/10 of the film thickness of the second layer.

[3. Polycarbonate resin substrate]
Any polycarbonate resin substrate in the polycarbonate resin laminate of the present invention can be used as long as the effects of the present invention are not impaired. The thickness of the polycarbonate resin substrate is also arbitrary depending on the use of the polycarbonate resin laminate, but is usually 100 μm or more, preferably 300 μm or more, more preferably 1 mm or more, and usually 20 mm or less, preferably The thing of 10 mm or less, More preferably, 8 mm or less can be used. It is preferable that the thickness is not less than the above-mentioned lower limit value because the uniformity of the thickness of the molded product is high.

  Here, the polycarbonate resin is produced by reacting one or more bisphenols that can contain a trihydric or higher polyhydric phenol as a copolymerization component with carbonates such as bisalkyl carbonate, bisaryl carbonate, and phosgene. As a copolymerization component, for example, an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid or a derivative thereof (for example, an aromatic dicarboxylic acid diester or aromatic) Dicarboxylic acid chloride) may be used.

  Examples of bisphenols include bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, and bisphenol Z (for abbreviations refer to the reagent catalog of Aldrich) and are available industrially. Among these, bisphenol A and bisphenol Z (in which the central carbon participates in the cyclohexane ring) are preferable, and bisphenol A is particularly preferable because it is easy.

Examples of copolymerizable trihydric phenols include 1,1,1- (4-hydroxyphenyl) ethane and phloroglucinol.
The polycarbonate resin may be used alone or in combination as two or more polymer blends, or may be a copolymer of plural types of monomers.

  There is no particular limitation on the production method of the polycarbonate resin. For example, (a) an organic solvent (for example, chlorinated chloride) which dissolves the polymer produced from an alkali metal salt of bisphenol and a carbonate derivative (for example, phosgene) active in nucleophilic attack (B) a polycondensation reaction in an organic base such as pyridine using bisphenols and a carbonate derivative active in nucleophilic attack as raw materials. A pyridine method, (c) a melt polymerization method in which bisphenols and a carbonate ester such as bisalkyl carbonate or bisaryl carbonate (preferably diphenyl carbonate) are used as raw materials, and (d) a bisphenol and carbon monoxide, Any known method such as a method of producing by reaction with carbon dioxide can be adopted. .

  The molecular weight of the polycarbonate resin is not particularly limited. For example, gel permeation chromatography using a chloroform solvent at 40 ° C. (single molecular weight dispersed polystyrene is used as a standard sample) as in the PMMA resin quality described in the reagent catalog of Aldrich. ) (Hereinafter abbreviated as “GPC”), the weight average molecular weight Mw measured is usually 10,000 or more, particularly 15,000 or more, more preferably 20,000 or more from the viewpoint of mechanical properties and melt fluidity. Moreover, it is usually 500,000 or less, preferably 200,000 or less, more preferably 100,000 or less.

The glass transition point Tg is usually 120 ° C. or higher, preferably from 130 ° C. or higher, more preferably 140 ° C. or higher from the viewpoint of heat resistance and melt fluidity, and is usually 190 ° C. or lower, preferably 180 ° C. or lower, more preferably. Is 170 ° C. or lower.

  The polycarbonate resin substrate is, for example, a polycarbonate resin typified by bisphenol A polycarbonate, or a polycarbonate polymer containing 30% by weight or more, preferably 50% by weight or more in terms of heat distortion resistance, impact resistance, and production cost. An alloy material, for example, a polycondensate of cyclohexanedimethanol and cyclohexanedicarboxylic acid, which is an alicyclic polyester, or a molded material having a film-like or plate-like portion made of a material obtained by blending a polyarylate resin with a polycarbonate resin. be able to.

The proportion of the polycarbonate resin in the constituent material of the polycarbonate resin substrate is preferably 50% by weight or more, more preferably 70% by weight or more in terms of the rigidity, surface hardness and heat distortion resistance (deflection temperature under load) of the polycarbonate resin substrate. In this constituent material, for example, an impact resistance improving agent such as an arbitrary elastomer or rubber and various additives may be contained.
Further, for example, heat stabilizers such as phosphites (for example, tris (2,4-di-tert-butylphenyl) phosphite commonly used under the trade name of MARK 2112), UV absorbers such as benzotriazole, plastics, etc. Additives such as agents, lubricants, release agents, pigments, antistatic agents, fillers, and the like may be mixed as appropriate. These may be used alone or in combination of two or more in any ratio and combination.

  For example, in order to improve the thermal stability at the time of molding, partial acrylation represented by hindered phenols such as Irganox 1010 and 1076 (manufactured by Ciba Geigy), Smither GS, and GM (manufactured by Sumitomo Chemical Co., Ltd.) Stabilizers such as phosphorus compounds represented by phosphites such as polyphenols and Irgaphos 168 (manufactured by Ciba Geigy) and additives such as long-chain aliphatic alcohols and long-chain aliphatic esters may be mixed. These may be used alone or in combination of two or more in any ratio and combination.

  The polycarbonate resin substrate can be produced by, for example, injection molding, extrusion molding, injection compression molding, hot press, vacuum press molding, solution casting, punching molding of a plate-like molded product, and the like.

  The light transmittance of the polycarbonate resin substrate itself is preferably 5% or more, more preferably 10% or more, and particularly preferably 20% or more. Higher light transmittance is preferred, but is practically preferably 95% or less, particularly preferably 90% or less. By setting the light transmittance to the above range, a polycarbonate resin laminate used for various applications as described later can be obtained.

[4. First layer]
The first layer may be a layer made of a composition containing a hydrolyzable silicon compound derivative and glass fiber.
Examples of the first layer forming method include a method of hydrolyzing the hydrolyzable silicon compound after applying a composition containing a hydrolyzable silicon compound and glass fiber on a polycarbonate resin substrate. . The coating method can be applied by any method such as dipping method, flow coating method, spray method, spin coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, offset method, and bar coating method. You can also The wet coating method is preferable because the film thickness of the first layer is easily uniform, and among these, the spin coating method is particularly preferable.

  The thickness of the first layer is arbitrary as long as the object and effect of the present invention are not impaired, but is usually 0.1 μm or more, preferably 1 μm or more, more preferably 3 μm or more. Moreover, it is 50 micrometers or less normally, Preferably it is 20 micrometers or less, More preferably, it is 10 micrometers or less. If it is above the above lower limit, it is preferable in that pinholes are hardly generated, and if it is below the above upper limit, it is preferable in that cracks are not easily generated during film hardening.

(Glass fiber)
The glass fiber used for the composition for forming the first layer is not particularly limited as long as the effects of the present invention are not impaired. For example, E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass). ), S glass (High strength glass) or alkali-resistant glass, and the like are melt-spun and formed into filamentous fibers. These may be used alone or in combination of two or more in any ratio and combination.

  Although there is no restriction | limiting in particular in the average fiber diameter of glass fiber, Usually, 0.1 micrometer or more, Preferably it is 1 micrometer or more, More preferably, it is 5 micrometers or more. Further, it is preferably 50.0 μm or less, more preferably 20 μm or less, and particularly preferably 15 μm or less. If it is at least the above lower limit, it is preferable because it is easy to produce at a low cost, and if it is not more than the above upper limit, the light transmittance of the polycarbonate resin laminate is likely to be high.

  The average fiber length is not particularly limited, but is preferably shorter from the viewpoint of transparency, and is preferably longer from the viewpoint of being less likely to cause in-film cracks. Preferably it is 1 micrometer or more, More preferably, it is 10 micrometers or more. Moreover, it is preferably 100 μm or less, more preferably 50 μm or less. It is preferable from the point of transparency that it is below the said upper limit.

  The glass fiber may be subjected to surface treatment or the like for improving dispersibility within a range not impairing the effects of the present invention. As a method of improving the dispersibility of the surface, any method may be used as long as it is a method of improving the hydrophilicity or dispersibility of the surface. Specifically, for example, epoxy-based, urethane-based, acrylic-based and And / or silane-based coupling treatment; immersion treatment in potassium dichromate-concentrated sulfuric acid mixed solution; surface hydrophilization treatment by plasma, and the like.

  The amount of glass fiber in the composition is usually 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and preferably 5% by weight or less, more preferably. Is 1% by weight or less. If it is at least the above lower limit, the occurrence of cracks in the film can be suppressed, and if it is not more than the above upper limit, the light transmittance of the polycarbonate resin substrate is preferred.

(Hydrolyzable silicon compound derivative)
The first hydrolyzable silicon compound derivative is obtained by hydrolyzing the hydrolyzable silicon compound. When a hydrolyzable silicon compound is heated in the presence of water, it may be hydrolyzed and further polycondensed. That is, the first layer of the polycarbonate resin laminate of the present invention contains a hydrolyzable silicon compound, this hydrolyzate, and this condensate. Examples of the hydrolyzable silicon compound include alkoxysilane.

As alkoxysilane, what is represented by the following general formula (I) is preferable.
R ¹ _n Si (OR ² ) _4-nGeneral formula (I)
Wherein R ¹ is an alkyl group having 1 to 18 carbon atoms which may contain halogen, an alkyl group having 1 to 6 carbon atoms including an amino group or a glycidyl group, a vinyl group, or a (meth) acryloyl group. R ² represents an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 to 3. When n is 2 or 3, R ¹ may be the same as or different from each other. In addition, when n is 0 to 2, R ² may be the same as or different from each other, provided that R ² may be partially a hydrogen atom.

Specific examples of the compound represented by the general formula (I) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, Methyltriacetoxysilane, methyltripropoxysilane, methyltriisopropenoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriacetoxy Silane, vinyltrimethoxyethoxysilane, vinyltriisopropenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloro Propyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltripropoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidoxypropyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ -(Meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- (β-aminoethyl) -γ- Aminopropyltrimeth Sisilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, diphenyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycid Xylpropylmethyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, γ-chloropropylmethyldimethoxysilane, γ -Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldie Toxisilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, trimethylmethoxysilane , Trimethylethoxysilane, trimethylisopropoxysilane and the like. These alkoxysilanes may be used individually by 1 type, and may mix and use 2 or more types by arbitrary ratios and combinations.
Among the alkoxysilanes, tetraethoxylane is particularly preferable.

  In addition, the water necessary for the hydrolysis of the hydrolyzable silicon compound is usually taken in moisture in the air, so it is not necessary to mix, but for the alkoxysilyl group of the hydrolyzable silicon compound, One equivalent or more is preferably present.

  The hydrolysis reaction may be performed in the presence of a catalyst. Examples of the catalyst include inorganic acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, acrylic acid, and methacrylic acid. Quaternary ammonium salts or trimethylamines of the above inorganic and organic acids; basic compounds represented by n-butylamine or salts thereof, acetylacetone aluminum, aluminum 2,2,6,6, -tetramethyl-3,5; -Heptanedionate, aluminum diisopropoxide ethyl acetoacetate, aluminum diisobutoxide ethyl acetoacetate, borate butoxide, dibutyltin dilaurate, dibutyltin dioctate and the like can be used. These can be used individually by 1 type or in combination of 2 or more types.

  The amount of the catalyst used is usually 0.0001 equivalents or more, preferably 0.001 equivalents or more, more preferably 0.01 equivalents or more with respect to 1 equivalent of the hydrolyzable silicon compound.

  The temperature at the start of hydrolysis or polycondensation is usually 20 ° C. or higher, preferably 30 ° C. or higher, more preferably 40 ° C. or higher, particularly preferably 60 ° C. or higher, usually 1 hour or longer, preferably 2 hours or longer, More preferably, it is made to react for 4 hours, Especially preferably, it is 6 hours or more, More preferably, it is made 48 hours or more.

When forming the first layer, a diluting solvent may be used. Examples of the diluent solvent include lower alcohols such as methanol, ethanol, propanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; diols such as ethylene glycol; and ethylene glycol monomethyl ether And cellosolves. Of these, lower alcohols are particularly preferred in that the hydrolysis of alkoxysilane proceeds smoothly.
These dilution solvents may be used individually by 1 type, and may be used as a mixed solvent which mixed 2 or more types by arbitrary ratios and combinations.

  When forming the first layer, a reaction accelerator for promoting the hydrolysis reaction may be used. Examples of the reaction accelerator include dimethylamine acetate, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, sodium propionate, sodium formate, benzyltrimethylammonium acetate, and the like. These may be used alone or in combination of two or more in any ratio and combination. The mixing amount of these reaction accelerators is usually 0.05% by weight or more and usually 1% by weight or less based on the hydrolyzable silicon group of the hydrolyzable silicon compound.

  In addition, various metal alkoxides, colloidal zinc oxides, zinc oxides, silicas, aluminas, titanium oxides, cerium oxides, tin oxides, antimony oxides, iron oxide fine particles, etc. A modifier or the like may be included in the raw material composition of the first layer. When components other than the hydrolyzable silicon compound and glass fiber are contained in the first layer raw material composition, the hydrolyzable silicon compound is usually contained in an amount of 30% by weight or more in the first layer raw material composition. .

  The first layer may contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include pigments, ultraviolet absorbers, antioxidants, flame retardants, fillers, leveling agents, and surfactants. These may be used alone or in combination of two or more in any ratio and combination.

[5. Second layer]
The second layer is a layer made of silica formed by an atmospheric pressure glow plasma method. As the atmospheric pressure glow plasma generator, a gas supply system, a discharge unit, a pulse-modulated high voltage, a high-frequency power source, a generator, a cooling system, etc. can be used, but is not limited thereto, Any atmospheric pressure glow plasma generator can be used as long as the effects of the present invention are not impaired.

An example of an atmospheric pressure glow plasma apparatus is shown in FIG. In the atmospheric pressure glow plasma generating apparatus 101 of FIG. 1, a high voltage power source is connected to the lower electrode 1 side. A water cooling system 5 is provided on the lower electrode 1 side.
The formation of the second layer is performed between two electrodes (lower electrode 1 and upper electrode 2) arranged in parallel in the atmospheric pressure glow plasma generator 101, that is, an area where an atmospheric pressure glow plasma discharge is formed (discharge area 3). The substrate 10 on which the first layer is formed is disposed, and glow plasma is generated in a state where the gas 4 serving as the material of the silica layer is supplied to the discharge region 3. A perforated plate 6 is disposed on the upper electrode 2 side of the atmospheric pressure glow plasma apparatus 101 shown in FIG. 1 in order to uniformly supply the gas 4 to the discharge region.

  The gas 4 that is the raw material of the silica layer is not necessarily a gas at normal temperature, and the supply method is appropriately selected depending on the temperature during atmospheric pressure glow plasma treatment and the state (solid, liquid, gas) at normal temperature. That is, when the gas is at the processing temperature and normal temperature, it is allowed to flow into the processing chamber as it is, or when it is liquid and has a relatively high vapor pressure, it is allowed to flow in as vapor or in bubbling with an inert gas or the like. Can be taken. On the other hand, when the vapor pressure is relatively low for liquids or solids, the gas or vapor pressure can be increased by heating to flow in.

  Examples of the raw material for the silica layer include alkoxysilane. These can be used individually by 1 type or in mixture of 2 or more types. Among the above raw materials, those having a small number of carbons bonded to Si are preferable because shrinkage caused by carbon desorption during formation of the silica film is reduced. Examples of the raw material for the silica film include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxylane, and diethyl. Diethoxysilane, trimethylmethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyl Oxypropylmethyldimethoxysilane, vinylorimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, p-vinylphenyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-P-styryltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltri Examples include methoxysilane. An alkoxysilane can be used individually or in combination of 2 or more types.

Among the above, from the viewpoint of crack suppression, tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), methyltriethoxysilane (CH ₃ Si (OC ₂ H ₅ ) ₃ ), dimethyldiethoxysilane ((CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ ), diethyldiethoxysilane ((C ₂ H ₅ ) ₂ Si (OC ₂ H ₅ ) ₂ ), and triethoxymethylsilane (CH ₃ Si (OC ₂ H ₅ ) ₃ ) Are preferable, and dimethyldiethoxysilane ((CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ ) and triethoxymethylsilane (CH ₃ Si (OC ₂ H ₅ ) ₃ ) are particularly preferable.

  In the case of using alkoxysilane as a raw material, usually, after heating in a predetermined container, bubbling with helium gas is performed to introduce gas 4 containing alkoxysilane into discharge region 3.

  As the carrier gas and the reactive gas, helium gas and oxygen gas are preferably used from the viewpoint of reactivity with the silica layer forming raw material. The amount of raw material alkoxysilane in the carrier gas is usually 0.05% to 4%. Further, the concentration of oxygen gas in the carrier gas is usually equal to or more than the amount of the raw material alkoxysilane and 5 times or less. That is, 0.05% to 20%.

  The voltage applied between the electrodes when the second layer is formed depends on the distance between the electrodes, but is usually set to a voltage value such that the discharge field has an electric field strength of 500 V / mm or more in terms of discharge stability.

  Further, the treatment time (glow plasma irradiation time) at the time of forming the second layer is usually 5 minutes or longer until the desired film thickness is reached although it depends on the concentration of the raw material alkoxysilane in the carrier gas.

  The preferred film thickness of the second layer is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1.0 μm or more. Further, it is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. It is preferable from the point of the hardness of a polycarbonate resin laminated body that it is more than the said minimum, and it is preferable from being less than the said upper limit since the crack of a film | membrane can be suppressed.

  The amount of carbon measured by the X-ray photoelectron spectroscopy (XPS) method in the second layer is preferably 5 atm% or less, more preferably 3 atm% or less, and particularly preferably 2 atm% or less. By making the amount of carbon in the second layer not more than the upper limit value, carbon atoms in the second layer raw material can be eliminated, and the hardness of the polycarbonate resin laminate can be increased, Further, the second layer can be reduced in cracks and the like. Analysis by X-ray photoelectron spectroscopy is performed using “PHI-5800ci” manufactured by ULVAC-PHI Co., Ltd.

[6. Primer layer]
The polycarbonate resin laminate of the present invention is not limited as long as the polycarbonate resin substrate, the first layer and the second layer are laminated in this order, but between the polycarbonate resin substrate and the first layer, the thermoplastic resin and More preferably, a primer layer containing a curable resin is formed. The primer layer may be any layer as long as it does not hinder the adhesion between the polycarbonate layer and the coating layer.
Therefore, the polycarbonate resin laminate of the present invention can have good appearance and high surface hardness, that is, excellent wear resistance and scratch resistance.

  As a specific example of providing a primer layer, a substrate layer adhesion property that increases the weather resistance of the polycarbonate resin laminate by forming a primer layer having high weather resistance between the polycarbonate resin substrate and the first layer. By forming a high primer layer, the adhesion between the polycarbonate resin substrate and the first layer is increased.

  When the primer layer is provided between the polycarbonate resin substrate and the first layer, the thickness of the primer layer is usually 100 μm or less, preferably 10 μm or less.

  The kind of thermoplastic resin and / or curable resin contained in the primer layer and the content in the primer layer are not limited as long as the purpose and effect of the present invention are not impaired, and are based on the performance required for the primer layer. Are appropriately selected.

When the thermoplastic resin contained in the primer layer is a polymer, it may be a homopolymer or a copolymer. Furthermore, when it is a copolymer, it may be a random copolymer or a block copolymer.
Examples of suitable thermoplastic resins include acrylic resins, polyester resins, phenoxy resins, and the like. These may be used alone or in combination of two or more in any ratio and combination. Among these, an acrylic resin is particularly preferable from the viewpoint of adhesiveness.

  Examples of the curable resin contained in the primer layer include an acrylic resin, an epoxy resin, and a urethane resin obtained by polymerizing an alkyl methacrylate monomer and a vinyl monomer. These may be used alone or in combination of two or more in any ratio and combination. Among these, acrylic resin is preferable from the viewpoint of adhesiveness.

  The primer layer containing the thermoplastic resin and / or the curable resin is a thermoplastic resin and / or a curable resin. Examples of the application method include a dipping method, a flow coating method, a spray method, a spin coating method, and a gravure coating. It can also be applied by any method such as a coating method, a roll coating method, a blade coating method, an air knife coating method, an offset method, or a bar coating method. Among these, the wet coating method is preferable because the film thickness of the first layer is easily uniform, and the spin coating method is particularly preferable.

  In order to impart desired characteristics to the primer layer according to the purpose, a known material mixed with the thermoplastic resin and / or the thermoplastic resin, for example, antioxidant, within a range not impairing the effect and purpose of the present invention. Stabilizers, heat stabilizers, UV absorbers, etc .; antistatic agents; flame retardants; flame retardant aids; colorants such as dyes and pigments; lubricants; plasticizers; crystallization accelerators; Silica or the like may be contained. You may use these individually by 1 type or 2 or more types by arbitrary ratios and combinations. When these components are contained in the primer layer, the total content of the thermoplastic resin and the curable resin in the primer layer is usually 80% by weight or more.

[7. Application]
Since the polycarbonate resin laminate of the present invention can be excellent in appearance, hardness, abrasion resistance, scratch resistance and light transmission, for example, a vehicle headlamp cover, windshield glass, vehicle window glass, etc. It is useful for roofing materials for vehicles, window glass for buildings, exterior wall materials for buildings, noise barriers for roads, face plates for displays, mobile phone members, and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof. Evaluation methods used in Examples and Comparative Examples are as follows.

[Martens hardness]
It is measured with an ultra-micro hardness meter (DUH-211 manufactured by Shimadzu Corporation), and the measured value when the indentation depth is 1/10 of the thickness of the second layer.

[Light transmittance]
It is set as the value measured about the light of wavelength 500nm with UV-spectrophotometer (JSCO V-650).

[Light transmittance retention after wear resistance test]
The initial light transmittance (before the test) and the light transmittance after the abrasion resistance test when the polycarbonate resin laminate was worn 100 times with a load of 1 kg using steel wool # 0000 by a Taber abrasion tester. The value obtained by dividing the difference by the initial light transmittance is taken as a value converted to 100%. The light transmittance is measured by the method described above.
[XPS analysis]
Measure using the above device.

[Example 1]
(Production of polycarbonate resin substrate)
A primer layer was formed on a polycarbonate resin substrate (Tg: 130 ° C., 30 mm × 40 mm, thickness 1 mm). The primer layer was prepared by dissolving polymethyl methacrylate (molecular weight 120,000 manufactured by ALDRICH) in propylene glycol monomethyl ether, applying a concentration of 30% with an applicator so that the film thickness after drying was 10 μm, and using hot air It is dry.

(Formation of the first layer)
Several micron glass fiber (Nippon Sheet Glass Co., Ltd. “CML-208” pulverized product, alkali-containing glass, average fiber diameter 0.8 μm) 0.01 g was adjusted to 5 ml (4.7 g) tetraethoxysilane. A composition for forming the first layer was obtained by sonication and dispersion. The composition was dropped on the primer layer using a micropipette and spin-coated at 2000 rpm. Thereafter, heat treatment was performed at 35 ° C. for 3 days in an incubator to obtain a 1.0 μm first layer.

(Formation of the second layer)
A helium and oxygen carrier gas is adjusted by a flow rate adjusting device to an atmospheric pressure glow plasma irradiation device equipped with a gas supply system, a discharge unit (500 W), a pulse-modulated high-voltage high-frequency power source (frequency 3 MHz), a cooling system, etc. and 2000 cm ³ · ^min -1 as the reaction gas ^was fed at a 1.04cm 3 · ^{min -1.} As a film forming source gas, diethyldiethoxysilane (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ (hereinafter also referred to as DEMS) is heated to 35 ° C. in a container and 1 cm ³ while bubbling with helium gas. A glow plasma discharge (applied voltage: 3 kV) was performed for 3 minutes by supplying the discharge part at a flow rate of min ⁻¹ . Thereby, a 1.6 μm second layer was formed. When the second layer was analyzed by XPS, C: 1.6 atm%, Si: 29.51 atm%, and O: 68.9 atm%.

(Evaluation)
The Martens hardness in the polycarbonate resin laminate was 500 Nmm ⁻² , and the light transmittance retention after the abrasion resistance test was 99.5%. Further, the haze value after the wear resistance test was 2.0%. When the presence or absence of cracks was confirmed by a scanning electron microscope (SEM), no cracks were confirmed.

[Example 2]
A polycarbonate resin laminate was formed in the same manner as in Example 1 except that the glow plasma discharge time of the second layer was 36 minutes. The film thickness of the second layer was 1.8 μm.
(Evaluation)
The Martens hardness in the polycarbonate resin laminate was 520 Nmm ⁻² , and the light transmittance retention after the abrasion resistance test was 99.5%. Further, the haze value after the wear resistance test was 1.8%. When the presence or absence of cracks was confirmed by a scanning electron microscope (SEM), no cracks were confirmed.

[Comparative Example 1]
A polycarbonate resin laminate was formed in the same manner as in Example 1 except that the first layer was not formed.
(Evaluation)
The Martens hardness in the polycarbonate resin laminate was 340 Nmm ⁻² and the light transmittance retention after the abrasion resistance test was 99.9%. Further, the haze value after the abrasion resistance test was 2.5%. When the presence or absence of cracks was confirmed by a scanning electron microscope (SEM), cracks were confirmed.

[Comparative Example 2]
A polycarbonate resin laminate was formed in the same manner as in Example 1 except that the glass fiber was not dispersed in the composition for forming the first layer.
(Evaluation)
The Martens hardness in the polycarbonate resin laminate was 500 Nmm ⁻² , and the light transmittance retention after the abrasion resistance test was 99.5%. Further, the haze value after the abrasion resistance test was 5%. When the presence or absence of cracks was confirmed by a scanning electron microscope (SEM), cracks were confirmed.

  Since the polycarbonate resin laminate of the present invention can be excellent in appearance, hardness (abrasion resistance and scratch resistance), and light transmittance, for example, a vehicle headlamp cover, a windshield, a vehicle window, etc. It can be used in various fields such as glass, vehicle roofing materials, window glass for buildings, exterior wall materials for buildings, soundproof walls for roads, face plates for displays, and members for mobile phones.

1: Lower electrode 2: Upper electrode 3: Discharge region 4: Gas 5: Water cooling system 6: Perforated plate 10: Substrate 101: Atmospheric pressure glow plasma generator

Claims (6)

A polycarbonate resin substrate, a first layer made of a composition containing a hydrolyzable silicon compound derivative and glass fiber, and a second layer made of silica formed by an atmospheric pressure glow plasma method are laminated in this order. A polycarbonate resin laminate characterized by the following. 2. The polycarbonate resin laminate according to claim 1, wherein the glass fiber content in the composition is 0.05% by weight or more and 5% by weight or less. The polycarbonate resin laminate according to claim 1 or 2, wherein the hydrolyzable silicon compound derivative is a hydrolyzate of tetraethoxysilane. The polycarbonate resin laminate according to any one of claims 1 to 3, wherein a carbon amount measured by an X-ray photoelectron spectroscopy (XPS) method on the surface of the second layer is 5 atm% or less. . The polycarbonate resin laminate according to any one of claims 1 to 4, wherein the second layer is formed using dimethyldiethoxysilane. The polycarbonate according to claim 1, further comprising a primer layer containing a thermoplastic resin and / or a curable resin between the polycarbonate resin substrate and the first layer. Resin laminate.

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