WO2020071379A1 - Substrat polymère doté d'une couche de revêtement dur - Google Patents

Substrat polymère doté d'une couche de revêtement dur

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Publication number
WO2020071379A1
WO2020071379A1 PCT/JP2019/038783 JP2019038783W WO2020071379A1 WO 2020071379 A1 WO2020071379 A1 WO 2020071379A1 JP 2019038783 W JP2019038783 W JP 2019038783W WO 2020071379 A1 WO2020071379 A1 WO 2020071379A1
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WIPO (PCT)
Prior art keywords
layer
group
silicon oxide
range
oxide layer
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PCT/JP2019/038783
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English (en)
Japanese (ja)
Inventor
浴中　達矢
孝志 依田
勝博 嘉悦
夢 武田
Original Assignee
帝人株式会社
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Application filed by 帝人株式会社 filed Critical 帝人株式会社
Priority to JP2020550462A priority Critical patent/JP7159336B2/ja
Publication of WO2020071379A1 publication Critical patent/WO2020071379A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor

Definitions

  • the present invention relates to a polymer substrate provided with a hard coat layer.
  • the present invention relates to a polymer substrate with a hard coat layer that has excellent wear resistance, weather resistance, high hardness, and heat resistance and can be used for a long period of time even under severe use environments.
  • This polymer substrate with a hard coat layer can be used, for example, for automotive window materials, building members, surface protection plates for solar cells, and the like.
  • resin moldings with high transparency are superior to inorganic glass in lightness, impact resistance, workability, formability with surrounding parts, design, etc. Taking advantage of these advantages, they have been widely used in various applications instead of inorganic glass.
  • these resins are inferior in surface abrasion resistance and hardness compared to inorganic glass, so they may be used as polymer substrates with hard coat layers in the form of laminated hard coat layers to prevent damage. Many.
  • polymer substrates with a hard coat layer for automotive windows have the mechanical strength required for window materials and the same abrasion resistance as inorganic glass to ensure visibility in driving safety.
  • environmental resistance that can withstand long-term outdoor exposure.
  • environmental resistance it has the ability to pass various tests assuming direct contact with moisture such as rainy weather, use in high humidity / dry environment, high / low temperature conditions, strong UV exposure, etc. There is a need. It can be said that the above proposals are still insufficient as a resin glazing material capable of stably achieving all of these required performances.
  • the abrasion resistance equivalent to inorganic glass for example, referring to standards such as the North American safety standard FMVSS205 and the European safety standard ECE R43, the abrasion resistance of windows used in parts that require visibility during operation
  • the property requirement is that the haze value increase ( ⁇ H) by a Taber abrasion test at 1000 rpm specified in ASTM D1044 is less than 2% or less than 2%.
  • boiling water resistance Resistance to the boiling water test (hereinafter referred to as boiling water resistance), which is an accelerated test for direct contact with moisture in the operating environment and long-term storage in a high-humidity environment, and high-temperature durability, which is an accelerated test for temperature changes in the operating environment Resistance to the test (hereinafter referred to as heat resistance) was often insufficient, and defects such as poor adhesion of the high-hardness hard coat layer, peeling phenomena, and crack generation were often observed.
  • thermosetting film of an acrylic resin, a thermosetting film of an organosiloxane resin, and a PE-CVD film using an organic silicon compound as a raw material are sequentially laminated on at least one surface of a plastic substrate.
  • the PE-CVD film has a gradient zone in which the abundance ratio of oxygen atoms and silicon atoms (O / Si ratio) increases from the interface with the thermosetting film of the organosiloxane resin and a substantially constant gradient zone following the gradient zone.
  • a plastic laminate comprising a flat zone is proposed.
  • Examples 1 and 2 include Taber abrasion performance of 2.0% or less and boiling water resistance by a boiling water immersion test of 2 hours, which are the targets of the present invention.
  • a laminate having both heat resistance at 1000C for 1000 hours is disclosed.
  • the immersion time in boiling water is 2 hours, but in order to ensure sufficient long-term reliability such as water resistance and moisture resistance, the immersion time in boiling water is at least 3 hours, more preferably 4 hours or more. I found that things were good.
  • the evaluation method of the adhesion test after immersion in boiling water it was found that the evaluation immediately after the test by the cross-cut tape method was insufficient, and it was necessary to confirm the evaluation at least 7 days after the test was performed. This is because the internal stress (compressive force in many cases) generated during the formation of the layer often remains in the silicon oxide layer formed by the PE-CVD method, and this action causes the separation of the layer over time. Was found to be seen.
  • a polymer substrate with a hard coat layer was immersed in boiling water at 100 ° C., kept for 3 hours, taken out of the boiling water, removed adhering water, left standing at room temperature for 2 hours, and compliant with JIS K5400.
  • An adhesion test is performed by a crosscut tape method.
  • a square having 10 ⁇ 10 cuts was formed into a cross-cut shape at 1 mm intervals with a cutter knife, and then a tape having a predetermined adhesive strength (for example, Nichiban Cellotape (trademark)) was attached and fixed. It is done in a form to be peeled off later.
  • Adhesion results immediately after the cross-cut tape test are referred to as “initial results”, and the results after 7 days from the cross-cut tape test are performed are “time-lapse results”. Only when the “time result” was also good, the adhesion performance and its reliability were determined to be good.
  • the “initial result” was good (100/100).
  • the hard coat layer was peeled off by the CVD method. That is, in the case of Example 1, the evaluation result was 70/100 (layer peeling occurred in 30 out of 100 squares), and in the case of Example 2, the result was 0/100 (layer peeling occurred in all 100 squares). The results were not satisfactory, and the performance needed to be improved.
  • infrared reflection technology and infrared absorption technology as the technology to cut off the infrared rays.
  • Infrared absorption technology among them can suppress the rise in the temperature inside the car, but the window itself becomes extremely hot. I will.
  • Patent Document 2 discloses a silicone coating composition
  • a silicone coating composition comprising an outermost layer (I) formed by plasma-polymerizing an organic silicon compound on an organic resin substrate, a composite oxide fine particle dispersion, a silicone resin, a curing catalyst, and a solvent.
  • a laminate having a plurality of coating layers including a lower layer (II) and optionally a lower layer (III) of an acrylic resin is proposed.
  • the target of the present invention is 2% or less.
  • a laminate having Taber abrasion performance is disclosed. It also discloses the correlation between individual physical properties and performance of each layer constituting the laminate.
  • Patent Document 3 a substrate, a first layer of a partial condensate of an organosiloxane, and plasma-polymerized organosilicon are deposited at a power level of 10 6 to 10 8 J / Kg under excess oxygen.
  • a multilayer product comprising a second layer is proposed, and Example 2 discloses the results of good appearance (no minute cracks) and good adhesion after a one-year outdoor exposure test in Florida, USA.
  • Nos. 4 and 5 disclose results of good appearance (no minute cracks) and good adhesion after a xenon weather-accelerated weathering test with an integrated radiation dose of 6875 KJ / m 2 .
  • Patent Document 4 a cured underlayer containing a hydrolysis-condensation product of an organic silicon compound as a main component and a PE-CVD method of an organic silicon compound are formed on the surface of a polymer substrate.
  • a polymer substrate with a hard coat in which a silicon oxide layer satisfying specific requirements is laminated has been proposed, and it has been disclosed that the heat resistance at 110 ° C. for 1000 hours was good, and that excellent boiling water resistance and weather resistance were obtained. Have been.
  • Patent Document 5 discloses a laminate in which a cured coating layer (I) of an active energy ray-curable primer composition and an inorganic material layer (II) are sequentially laminated on a resin substrate,
  • the line-curable primer composition is (A) a silsesquioxane compound having an organic group directly bonded to a silicon atom, and at least one of the organic groups is an organic group having a (meth) acryloyloxy group.
  • a structure containing a silsesquioxane compound and (B) a photopolymerization initiator wherein the inorganic material layer (II) is formed by a dry film formation method.
  • Patent Document 6 a first hard coat layer made of an ultraviolet-curable resin, an anchor coat layer made of an organic-inorganic hybrid resin, and an organic silicon-based or organic aluminum-based reaction gas during chemical vapor deposition are applied to a base film. And a second hard coat layer having high scratch resistance obtained by forming a film using the same.
  • Patent Document 7 discloses an organic resin base material and a multilayer coating layer on the surface of the base material, wherein the multilayer coating layer is the outermost layer of a hard coating obtained by plasma-polymerizing an organic silicon compound ( I) and an intermediate layer (II) of a cured film formed from the composite coating composition (2), wherein one surface of the intermediate layer (II) is in contact with the outermost layer and the other surface is in contact with the organic resin base material.
  • (2) inorganic oxide nanoparticles comprising (2-A) one selected from silica, zinc oxide, titanium oxide, cerium oxide, and a combination comprising at least one of the foregoing.
  • (2-B) a vinyl copolymer having an organic ultraviolet absorbing group and a reactive group selected from an alkoxysilyl group, a hydroxyl group, an epoxy group, a carboxylic acid group and an amino group, and (2-B) ) Contains a solvent, organic resin laminate is disclosed having a weather resistance and scratch resistance.
  • Patent Document 8 discloses a laminate in which a resin layer (I) of an active energy ray-curable resin composition and an inorganic oxide vapor-deposited film layer (II) are provided in this order. There is disclosed a laminate characterized in that the resin composition contains a composite resin used in the cured underlayer of the present invention.
  • the present invention relates to a polymer substrate with a hard coat layer having a hard layer formed by laminating a high-hardness hard coat layer by a plasma-induced chemical vapor deposition (PE-CVD) method on the surface layer.
  • PE-CVD plasma-induced chemical vapor deposition
  • the present invention is as follows with respect to solving the above-mentioned problems.
  • the cured underlayer has a thickness of 1 to 20 ⁇ m and contains 10 to 90 parts by weight of a polyfunctional acrylate, 90 to 10 parts by weight of inorganic oxide fine particles and / or a hydrolyzed condensate of a silicon compound.
  • a condensate is an essential component
  • the silicon compound hydrolytic condensate has a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group.
  • R 4 is Represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or an aralkyl having 7 to 12 carbon atoms.
  • R 1 , R 2 and R 3 is a group having the above-mentioned polymerizable double bond
  • a carbon atom forms a part of the vinyl polymer segment (a2)
  • a silicon atom bonded only to an oxygen atom forms a part of the polysiloxane segment (a1).
  • the silicon oxide layer satisfies all of the following requirements (a 1 ) to (c 1 ) at a position of 0.04 ⁇ m in the thickness direction from the interface between the hardened base layer and the silicon oxide layer, and Satisfies all of the following requirements (b 3 ) to (c 3 ) on the surface opposite to Polymer substrate with hard coat layer according to ⁇ 1>:
  • (A 1 ) When the chemical composition is represented by SiO x C y H z , x is in the range of 1.93 to 1.98, y is in the range of 0.04 to 0.15, and z is Being in the range of 0.10 to 0.45,
  • (B 1) IR absorbance ratio of the wave number 930 cm -1 and 1020cm -1 ( ⁇ 930 / ⁇ 1020 ) may be in the range of 0.10-0.20,
  • (C 1) IR absorbance ratio of the wave number 1280 cm -1 and 1020cm -1 ( ⁇ 1280 / ⁇ 1020 ) may be in the range
  • y in (a 3 ) is larger by 0.02 to 0.10 than y in (a 1 ), and z in (a 3 ) is 0.05 more than z in (a 1 ).
  • the base cured layer contains a (meth) acrylic resin containing 0.1 to 5 mol / kg of at least one selected from a hydroxyl group, an amino group, a carboxyl group and an alkoxysilyl group in a compound.
  • ⁇ 5> The polymer substrate with a hard coat layer according to any one of ⁇ 1> to ⁇ 4>, wherein the inorganic oxide fine particles have a primary particle size of 1 nm to 200 nm.
  • ⁇ 6> The polymer substrate with a hard coat layer according to any one of ⁇ 1> to ⁇ 5>, wherein the polymer substrate is a polycarbonate resin substrate.
  • ⁇ 7> The polymer substrate with a hard coat layer according to any one of ⁇ 1> to ⁇ 6>, wherein the silicon oxide layer is a plasma CVD layer.
  • the silicon oxide layer has a thickness of 2.5 to 9 ⁇ m, and the following (a 2 ) to (c 2 ) are located at 2.0 ⁇ m in the thickness direction from the interface between the hardened underlayer and the silicon oxide layer.
  • the polymer substrate with a hard coat layer according to any one of ⁇ 1> to ⁇ 7>, which satisfies all the requirements of (1):
  • (A 2 ) When the chemical composition is represented by SiO x C y H z , x is in the range of 1.81 to 1.90, y is in the range of 0.15 to 0.32, and z is In the range of 0.45 to 0.90,
  • B 2 Infrared absorbance ratio of the wave number 930 cm -1 and 1020cm -1 ( ⁇ 930 / ⁇ 1020 ) may be in the range of 0.21 to 0.36,
  • (C 2) Infrared absorbance ratio of the wave number 1280 cm -1 and 1020cm -1 ( ⁇ 1280 / ⁇ 1020 ) may be
  • ⁇ 12> Between a portion of the silicon oxide layer satisfying all the requirements (a 2 ) to (c 2 ) and a portion of the silicon oxide layer satisfying all the requirements of (a 3 ) to (c 3 ) ⁇ 8> further includes a gradient layer in which the change in the value of the x, the y, the z, the ⁇ 930 / ⁇ 1020 , and / or the ⁇ 1280 / ⁇ 1020 is gradient.
  • ⁇ 13> The polymer substrate with a hard coat layer according to any one of ⁇ 1> to ⁇ 7>, wherein the thickness of the silicon oxide layer is 0.1 to 2.5 ⁇ m.
  • FIG. 1 is a schematic view of an example of a capacitively coupled PE-CVD apparatus that can be used for forming a silicon oxide layer by the PE-CVD method of the present invention.
  • FIG. 2 is a schematic view of another example of a capacitive coupling type PE-CVD apparatus that can be used for forming a silicon oxide layer by the PE-CVD method of the present invention.
  • FIG. 3A is an example of a reactive gas introduction head provided on an electrode in a capacitively coupled PE-CVD apparatus that can be used for forming a silicon oxide layer by the PE-CVD method of the present invention, and
  • FIG. b) shows an arrangement (an example) of a large number of gas ejection holes provided on the surface facing the substrate to be processed.
  • 1 is a schematic cross-sectional view of a polymer substrate with a hard coat layer applied to one embodiment of the present invention. It is a cross section of a polymer substrate with a hard coat layer applied to another embodiment of the present invention.
  • an under-cured layer 70 and a silicon oxide layer 80 formed by PE-CVD are laminated in this order on at least one surface of the polymer substrate 50.
  • lamination of the layer on the other side is not always essential, and a preferable configuration is selected according to the application and necessity.
  • another layer may not be present on the other surface of the polymer substrate 50.
  • a layer other than the adhesive layer 60, the underlying cured layer 70, and the silicon oxide layer 80 by PE-CVD for example, an ultraviolet curable resin layer). , Etc.
  • Polymer substrate 50 examples of the material of the polymer substrate 50 include acrylic resins such as polycarbonate resin and polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and poly (ethylene-2,6-naphthalate), polystyrene resins, polypropylene resins, and polyarylate. Resin, polyethersulfone resin, ABS resin, polylactic acid resin, and the like. These resins can be used alone or in combination of two or more. Among these, polycarbonate resins having excellent transparency, heat resistance, impact resistance, and the like are particularly preferable when used for automobile windows. More preferably, the polymer substrate is an acrylic-coated polycarbonate substrate coextruded with an acrylic resin for covering the surface together with the polycarbonate resin.
  • the heat distortion temperature (HDT) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 130 ° C. or higher.
  • the polycarbonate resin is, for example, a polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melting method.
  • the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4 -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 9,9-bis ⁇ (4-hydroxy-3-methyl) phenyl ⁇ fluorene, 2,2-bis (4-hydroxy Phenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1
  • carbonate precursor carbonyl halide, carbonate ester or haloformate
  • specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like.
  • a catalyst, a terminal stopper, an antioxidant for a dihydric phenol, and the like may be used as necessary. May be used.
  • the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.
  • the molecular weight of the polycarbonate resin is preferably 10,000 to 50,000, more preferably 15,000 to 35,000 in terms of viscosity average molecular weight (M).
  • M viscosity average molecular weight
  • a polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength is obtained and the melt fluidity during molding is good.
  • the viscosity average molecular weight referred to in the present invention is determined by inserting the specific viscosity ( ⁇ sp ) obtained from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
  • polycarbonate resin examples include various copolymerized polycarbonates such as a polycarbonate resin obtained by copolymerizing isosorbide and an aliphatic diol, and a polycarbonate-polyorganosiloxane copolymer.
  • Such a polycarbonate resin may include, if necessary, a stabilizer such as a phosphite, a phosphate or a phosphonate, a low molecular weight polycarbonate such as tetrabromobisphenol A, a tetrabromobisphenol A, a flame retardant such as decabromodiphenol, a benzotriazole.
  • a stabilizer such as a phosphite, a phosphate or a phosphonate
  • a low molecular weight polycarbonate such as tetrabromobisphenol A, a tetrabromobisphenol A
  • a flame retardant such as decabromodiphenol, a benzotriazole.
  • UV absorbers such as benzophenones, triazines and salicylates; inorganic UV absorbers such as titanium oxide, cerium oxide and zinc oxide; cyanine compounds, squalilium compounds, thiol nickel complex salt compounds, phthalocyanine compounds Compounds, triallylmethane compounds, naphthoquinone compounds, anthraquinone compounds, carbon black, antimony oxide, tin oxide doped with indium oxide, infrared shielding agents such as lanthanum boride, coloring agents, lubricants, etc. Combined and can be used.
  • the thickness of the polymer substrate is preferably in the range of 1 to 20 mm. If the thickness is less than 1 mm, it is difficult to maintain the required mechanical strength of window materials for automobiles and the like, and the lamination of the silicon oxide layer by the PE-CVD method increases the flexural deformation of the substrate, causing problems in dimensional stability and appearance. This often occurs and is not preferred. On the other hand, when the thickness is more than 20 mm, it is difficult to obtain a molded substrate having surface smoothness required as a window material and having small optical distortion (such as perspective distortion), and the substrate weight is increased. Not preferred.
  • the thickness of the polymer substrate is more preferably 2 to 10 mm, and still more preferably 3 to 7 mm.
  • the base cured layer 70 of the first embodiment is laminated on the surface of the polymer substrate, contains a silicon compound hydrolyzed condensate, and the silicon compound hydrolyzed condensate is formed by the general formula (1) and / or
  • the polysiloxane segment (a1) having a structural unit represented by the general formula (2), a silanol group and / or a hydrolyzable silyl group, and the vinyl polymer segment (a2) are formed by the general formula ( It contains the composite resin (A) bound by the bond represented by 3) and has a thickness of 1 to 20 ⁇ m. This thickness may be, for example, 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, and may be 20 ⁇ m or less, 15 ⁇ m or less, or 10 ⁇ m or less.
  • the underlayer cured layer (70) is composed of 10 to 90 parts by weight of a polyfunctional acrylate having two or more (meth) acryloyl groups in one molecule, and the sum of any inorganic oxide fine particles and a silicon compound hydrolyzed condensate. It is preferably a layer obtained by heat curing or active energy ray curing of a precursor composition containing 90 to 10 parts by weight (hereinafter, referred to as a precursor composition), particularly a layer obtained by active energy ray curing. Is preferred.
  • (meth) acrylate refers to one or both of acrylate and methacrylate
  • (meth) acryloyl group refers to one or both of an acryloyl group and a methacryloyl group.
  • Examples of the optionally used polyfunctional (meth) acrylate include trimethylolpropane di (meth) acrylate, ethylene oxide-modified trimethylolpropane di (meth) acrylate, propylene oxide-modified trimethylolpropane di (meth) acrylate, and glycerin diacrylate.
  • (meth) acrylates can be used, but it is preferable to use two or more of them in combination to balance hardness and flexibility. Further, among these (meth) acrylates, it is preferable that pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate are blended in a certain amount to improve the scratch resistance.
  • the inorganic oxide fine particles optionally used for example, titanium oxide, zinc oxide, cerium oxide, silicon oxide and the like can be mentioned.
  • the primary particle size of the inorganic oxide fine particles is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm. The above range is preferable because a cured underlayer having excellent transparency and weather resistance can be formed.
  • the silicon compound hydrolyzed condensate is a polysiloxane segment (a1) having a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group. (Hereinafter simply referred to as a polysiloxane segment (a1)) and a vinyl polymer segment (a2) (hereinafter simply referred to as a vinyl polymer segment (a2)) represented by the general formula (3). Containing the composite resin (A) bonded by Here, the polysiloxane segment (a1) is an essential component of the structural unit represented by the general formula (1) and / or the general formula (2), but the vinyl polymer segment (a2) is also an essential component. And the structural unit represented by the general formula (1) and / or the general formula (2). Examples of the composite resin (A) include resins described in paragraphs 0035 to 0087 of Patent Document 8. This document is incorporated by reference.
  • the base cured layer 70 may be substantially composed of only a silicon compound hydrolyzed condensate containing the composite resin (A). It is preferably composed of a functional acrylate, and more preferably contains a composite resin (A), a polyfunctional acrylate, and inorganic oxide fine particles.
  • the composite resin (A) used in the present invention is a polysiloxane having a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group.
  • the bond represented by the general formula (3) has hydrolysis resistance and is excellent in long-term weather resistance.
  • a dehydration condensation reaction occurs between a silanol group and / or a hydrolyzable silyl group of the polysiloxane segment (a1) described below and a silanol group and / or a hydrolyzable silyl group of the vinyl polymer segment (a2) described later.
  • the bond represented by the general formula (3) is generated. Therefore, in the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1).
  • Examples of the form of the composite resin (A) include a composite resin having a graft structure in which the polysiloxane segment (a1) is chemically bonded as a side chain of the polymer segment (a2), or the polymer segment (a2). And the above-mentioned polysiloxane segment (a1).
  • the polysiloxane segment (a1) in the present invention is a segment having a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group.
  • the structural unit represented by the general formula (1) and / or the general formula (2) contains a group having a polymerizable double bond.
  • the structural unit represented by the general formula (1) and / or the general formula (2) has a group having a polymerizable double bond as an essential component.
  • R 1 , R 2 and R 3 is a group having the above-mentioned polymerizable double bond.
  • the alkylene group having 1 to 6 carbon atoms for R 4 include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, Pentylene group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohexylene group, 1-methylpentylene Benzene, 2-methylpentylene, 3-methylpentylene, 1,1-dimethylbutylene, 1,2-dimethylbutylene, 2,2-dimethyl
  • the alkyl group having 1 to 6 carbon atoms includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl Group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl Group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2 , 2-trimethylpropyl group, 1-ethyl-2-methylpropyl group, 1-ethy
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
  • Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
  • R 1 , R 2 and R 3 are a group having a polymerizable double bond
  • the polysiloxane segment (a1) is represented by the general formula (1) when having the structural unit is a group R 1 has a polymerizable double bond
  • having the structural unit of polysiloxane segment (a1) is represented by the general formula (2) R 2 and And / or when R 3 is a group having a polymerizable double bond and the polysiloxane segment (a1) has both the structural units represented by the general formulas (1) and (2), It shows that at least one of 1 , R 2 and R 3 is a group having a polymerizable double bond.
  • two or more polymerizable double bonds are preferably present in the polysiloxane segment (a1), more preferably 3 to 200, and still more preferably 3 to 50.
  • a coating film having excellent durability can be obtained.
  • the content of the polymerizable double bond in the polysiloxane segment (a1) is 3 to 35% by weight, desired weather resistance and adhesion can be obtained.
  • the term "polymerizable double bond" as used herein is a general term for a vinyl group, a vinylidene group or a vinylene group capable of performing a growth reaction by a free radical.
  • the content of the polymerizable double bond indicates the weight% of the vinyl group, vinylidene group or vinylene group in the polysiloxane segment.
  • the group having a polymerizable double bond all known functional groups containing the vinyl group, vinylidene group and vinylene group can be used.
  • the structural unit represented by the general formula (1) and / or the general formula (2) is a three-dimensional network-like polysiloxane structural unit in which two or three of the silicon bonds are involved in crosslinking. Since a dense network structure is not formed even though a three-dimensional network structure is formed, gelation or the like does not occur during production or formation of a primer, and storage stability is improved.
  • the silanol group is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom.
  • the silanol group is a silanol group formed by bonding an oxygen atom having a bond to a hydrogen atom in the structural unit represented by the general formula (1) and / or the general formula (2).
  • the hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specifically includes, for example, a group represented by the general formula (4). .
  • R 5 represents a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group
  • R 6 represents a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, tert- butyl group, a pentyl group, isopentyl group, neopentyl group, tert -Pentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl Group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group , 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group and the
  • Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
  • Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
  • the halogen atom e.g., fluorine atom, chlorine atom, bromine atom, and an iodine atom.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, and a tertiary butoxy group.
  • the acyloxy group include, for example, formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, naphthoyloxy and the like.
  • Examples of the aryloxy group include phenyloxy and naphthyloxy.
  • Examples of the alkenyloxy group include a vinyloxy group, an allyloxy group, a 1-propenyloxy group, an isopropenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, a 2-petenyloxy group, a 3-methyl-3-butenyloxy group, -Hexenyloxy group and the like.
  • the hydrolyzable silyl group represented by the general formula (4) becomes a silanol group.
  • a methoxy group and an ethoxy group are preferable because of excellent hydrolyzability.
  • the hydrolyzable silyl group is formed by bonding an oxygen atom having a bond of the structural unit represented by the general formula (1) and / or the general formula (2) to the hydrolyzable group.
  • it is preferably a substituted hydrolyzable silyl group.
  • the silanol group or the hydrolyzable silyl group is formed by a curing reaction of the group having a polymerizable double bond, a hydroxyl group or a hydrolyzable silyl group in the silanol group is formed in parallel with the curing reaction. Since the hydrolysis-condensation reaction proceeds between the hydrolyzable groups in the group, the crosslink density of the polysiloxane structure of the resulting coating film increases, and a coating film having excellent solvent resistance and the like can be formed. Further, the polysiloxane segment (a1) containing the silanol group or the hydrolyzable silyl group and the vinyl polymer segment (a2) described below are bonded via a bond represented by the general formula (3). Used when
  • the polysiloxane segment (a1) is not particularly limited except that it has a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group. , And may contain other groups.
  • Polysiloxanes R 1 in the general formula (1) is a structural unit is a group having a polymerizable double bond
  • R 1 in the general formula (1) coexist and the structural unit is an alkyl group such as methyl It may be a segment (a1)
  • a structural unit R 1 is an alkyl group such as a methyl group and structural units R 1 is a group having a polymerizable double bond in the formula (1)
  • R 2 and R 3 in may be a polysiloxane segments coexist a structural unit is an alkyl group such as a methyl group (a1)
  • the structural unit in which R 1 in the general formula (1) is a group having the polymerizable double bond and the structural unit in which R 2 and R 3 in the general formula (2) are an alkyl group such as a methyl group are included.
  • the coexisting polysiloxane segment (a1) may be used, and there is no particular limitation. Specifically, examples of the polysiloxan
  • the polysiloxane segment (a1) preferably contains 10 to 65% by weight based on the total solid content of the active energy ray-curable resin composition constituting the resin layer (I). It is possible to achieve both the adhesion to the material and the inorganic oxide vapor-deposited film layer (II) and the weather resistance.
  • the vinyl polymer segment (a2) in the present invention is a vinyl polymer segment such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer, and a polyolefin polymer.
  • an acrylic polymer segment is preferred because the resulting coating film is excellent in transparency and gloss.
  • the acrylic polymerizable segment is obtained by polymerizing or copolymerizing a general-purpose (meth) acrylic monomer.
  • the (meth) acrylic monomer is not particularly limited, and a vinyl monomer can also be copolymerized.
  • the vinyl polymer segment (a2) in the present invention is more preferably a (meth) acrylic repeating unit having a cyclic hydrocarbon group from the viewpoint of improving adhesion to a plastic substrate.
  • the (meth) acrylic repeating unit having a cyclic hydrocarbon group preferably, cyclohexyl (meth) acrylate, cyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclododecanyl ( (Meth) acrylates having a cyclic hydrocarbon group, such as (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl acrylate. These can be used alone or in combination of two or more.
  • the vinyl polymer segment (a2) can be obtained by a known method.
  • 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-) are obtained by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization.
  • the vinyl polymer segment (a2) can be obtained by using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate.
  • the number average molecular weight of the vinyl polymer segment (a2) is preferably in the range of 500 to 200,000 in terms of number average molecular weight (hereinafter abbreviated as Mn), and the composite resin (A) is produced. It is possible to prevent thickening and gelation at the time of performing, and it is excellent in durability. Mn is more preferably in the range of 700 to 100,000, and still more preferably in the range of 1,000 to 50,000 in view of the suitability for coating and adhesion to the substrate described below.
  • the vinyl-based polymer segment (a2) is a vinyl-based polymer segment (a) in order to form a composite resin (A) bonded to the polysiloxane segment (a1) by a bond represented by the general formula (3). It has a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond in a2). Since these silanol groups and / or hydrolyzable silyl groups become bonds represented by the general formula (3) in the production of the composite resin (A) described below, the composite resin (A )) Hardly exists in the vinyl polymer segment (a2).
  • the vinyl-based polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is, specifically, the general-purpose monomer and the silanol group and / or directly bonded to a carbon bond. It is obtained by copolymerizing with a vinyl monomer containing a hydrolyzable silyl group.
  • Examples of the vinyl monomer having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyltri (2-methoxyethoxy) silane.
  • the vinyl polymer segment (a2) preferably has an alcoholic hydroxyl group.
  • the vinyl polymer segment (a2) having an alcoholic hydroxyl group can be obtained by copolymerizing a (meth) acrylic monomer having an alcoholic hydroxyl group.
  • Specific examples of the (meth) acrylic monomer having an alcohol hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
  • the amount of the alcoholic hydroxyl group is appropriately determined by calculating from the amount of polyisocyanate (B) to be described later. Further, as described later, in the present invention, it is more preferable to use an active energy ray-curable monomer having an alcoholic hydroxyl group in combination. Therefore, the amount of the alcoholic hydroxyl group in the vinyl polymer segment (a2) having an alcoholic hydroxyl group can be determined in consideration of the amount of the active energy ray-curable monomer having an alcoholic hydroxyl group used in combination. It is preferable that the content is substantially in the range of 30 to 300 in terms of the hydroxyl value of the vinyl polymer segment (a2).
  • the composite resin (A) used in the present invention is specifically produced by the following (method 1) to (method 3).
  • Method 1 The general-purpose (meth) acrylic monomer or the like and the vinyl-based monomer having a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon bond are copolymerized to directly bond to the carbon bond.
  • a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group is obtained.
  • This is mixed with a silane compound having both a silanol group and / or a hydrolyzable silyl group and a polymerizable double bond and, if necessary, a general-purpose silane compound, and subjected to a hydrolysis-condensation reaction.
  • a silanol group and / or a hydrolyzable silyl group and a silanol group or a hydrolyzable silyl group of a silane compound having a polymerizable double bond are combined with a silanol group and / or a hydrolyzable group directly bonded to a carbon bond.
  • the silanol group and / or the hydrolyzable silyl group of the vinyl polymer segment (a2) containing a hydrophilic silyl group undergoes a hydrolysis-condensation reaction to form the polysiloxane segment (a1) and the polysiloxane.
  • the composite resin (A) in which the segment (a1) and the vinyl polymer segment (a2) are composited by the bond represented by the general formula (3) is obtained.
  • Method 2 In the same manner as in Method 1, a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is obtained.
  • a silane compound having both a silanol group and / or a hydrolyzable silyl group and a polymerizable double bond and, if necessary, a general-purpose silane compound are subjected to a hydrolytic condensation reaction to obtain a polysiloxane segment (a1).
  • Method 3 In the same manner as in Method 1, a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is obtained. On the other hand, in the same manner as in Method 2, a polysiloxane segment (a1) is obtained. Further, a silane compound containing a silane compound having a polymerizable double bond and, if necessary, a general-purpose silane compound are mixed and subjected to a hydrolytic condensation reaction.
  • Examples of the silane compound having a silanol group and / or a hydrolyzable silyl group and a polymerizable double bond used in the above-mentioned (method 1) to (method 3) include, specifically, vinyltrimethoxysilane, Vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethylvinylether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (Meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane and the like can be mentioned. Among them, vinyltrimethoxysilane and 3- (meth) acryloyloxyprop
  • Examples of general-purpose silane compounds used in (Method 1) to (Method 3) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyl
  • organotrialkoxysilanes such as trimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane
  • Diorganodialkoxysilanes such as dimethyldimethoxysilane, diphenyldimethoxysilane, methylcyclohexyldimethoxysilane or methylphenyldimethoxysilane; methylt
  • a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra-n-propoxysilane or a partially hydrolyzed condensate of the tetrafunctional alkoxysilane compound may be used in combination as long as the effects of the present invention are not impaired. it can.
  • the silicon atoms of the tetrafunctional alkoxysilane compound are 20% of the total silicon atoms constituting the polysiloxane segment (a1). It is preferable to use them together so as not to exceed the mol%.
  • a metal alkoxide compound other than a silicon atom such as boron, titanium, zirconium or aluminum can be used in combination with the silane compound as long as the effects of the present invention are not impaired.
  • a metal alkoxide compound in combination with the above metal alkoxide compound in an amount not exceeding 25 mol% with respect to all silicon atoms constituting the polysiloxane segment (a1).
  • a part of the hydrolyzable group is hydrolyzed under the influence of water or the like to form a hydroxyl group, and then the hydroxyl groups are hydrolyzed with each other or with the hydroxyl group. It refers to a progressing condensation reaction that progresses with an ionic group.
  • the hydrolysis-condensation reaction can be carried out by a known method, but a method in which the reaction is carried out by supplying water and a catalyst in the production step is simple and preferable.
  • the catalyst to be used examples include: inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate And titanates such as tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), Compounds containing various basic nitrogen atoms, such as 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole and 1-methylimidazole; Tetramethyl ammonium salt, tetrabutyl ammonium salt, dilauryl dimethyl ammonium Various quaternary am
  • the amount of the catalyst to be added is not particularly limited, but it is generally preferable to use the catalyst in an amount of 0.0001 to 10% by weight based on the total amount of each of the compounds having a silanol group or a hydrolyzable silyl group. , More preferably in the range of 0.0005 to 3% by weight, and particularly preferably in the range of 0.001 to 1% by weight.
  • the amount of water to be supplied is preferably 0.05 mol or more, and more preferably 0.1 mol, per 1 mol of the silanol group or the hydrolyzable silyl group of each compound having the silanol group or the hydrolyzable silyl group.
  • the above is more preferable, and particularly preferably 0.5 mol or more.
  • These catalyst and water may be supplied collectively or sequentially, or a mixture of the catalyst and water in advance may be supplied.
  • the reaction temperature for performing the hydrolysis-condensation reaction in the above (Method 1) to (Method 3) is suitably in the range of 0 ° C to 150 ° C, preferably in the range of 20 ° C to 100 ° C. Further, the reaction can be carried out under any conditions of normal pressure, increased pressure or reduced pressure. In addition, alcohol and water, which are by-products generated in the hydrolysis and condensation reaction, may be removed by a method such as distillation as needed.
  • the charge ratio of each compound in (Method 1) to (Method 3) is appropriately selected depending on the desired structure of the composite resin (A) used in the present invention. Above all, it is preferable to obtain the composite resin (A) so that the content of the polysiloxane segment (a1) is 30 to 95% by weight because the durability of the obtained coating film is excellent, and 30 to 75% by weight is preferable. More preferred.
  • the vinyl polymer segment is examples of the method include a method in which a silanol group and / or a hydrolyzable silyl group of the polysiloxane segment and a silanol group and / or a hydrolyzable silyl group of the polysiloxane segment described above are subjected to a hydrolytic condensation reaction.
  • the cured undercoat layer prepared in this manner is subjected to subsequent surface treatment such as plasma treatment (atmospheric pressure, vacuum), flame treatment, corona treatment, UV (150 to 400 nm) (ozone) treatment, chemical treatment, and the like.
  • plasma treatment atmospheric pressure, vacuum
  • flame treatment corona treatment
  • UV (150 to 400 nm) (ozone) treatment UV (150 to 400 nm) (ozone) treatment
  • chemical treatment and the like.
  • Part of the components decomposes and disappears, and the proportion of the inorganic components increases inclining toward the surface, achieving an extremely good surface to ensure adhesion to the silicon oxide layer by PE-CVD. it can.
  • the surface of the under-cured layer has a water contact angle of 35 ° or less, and the surface roughness when measured by a DFM method under an observation condition of 5 ⁇ m square.
  • Ra is preferably in the range of 0.7 to 10.0 nm. Since the underlying hardened layer also often becomes electrically insulating, the DFM method is effective for observing the surface thereof, as described later.
  • the water contact angle reflects the magnitude of the intermolecular force with the polar substance on the polymer substrate surface.
  • liquid such as water on a solid surface becomes a sphere because the surface area is reduced if there is no intermolecular force with the surface, but if intermolecular force (surface energy) acts between the solid surface and water, water becomes It spreads on the solid surface in order to obtain and stabilize more surface energy, and the contact angle is reduced.
  • intermolecular force surface energy
  • the silicon oxide layer formed by the PE-CVD method is also a layer having a high polarity, a large amount of surface energy is obtained and stabilized from a solid surface having a low water contact angle.
  • a water contact angle of 35 ° or less on the substrate surface of the present invention is preferable because sufficient adhesion to the silicon oxide layer can be obtained.
  • the surface roughness measured by the DFM method reflects the surface smoothness at the nano-size level of the surface of the base hardened layer, but the surface roughness is not sufficient for enhancing the adhesion to the silicon oxide layer by the PE-CVD method. It is preferable that an appropriate shape of the surface irregularities defined in the preferable range exists. Surface irregularities refer to those observed by the DFM method as single or interconnected pores and / or projections. The presence of these surface irregularities enhances the anchor effect (wedge effect) related to the improvement of adhesion. It is considered to be.
  • the surface roughness (Ra) of the base cured layer surface of the present invention is less than 0.7 nm, the effect of improving the adhesion is hardly obtained.
  • the surface roughness (Ra) exceeds 10.0 nm, the mechanical strength of the base cured layer surface is reduced, and as a result, In some cases, this may lead to a decrease in adhesion, which is not preferable.
  • the surface roughness (Ra) of the surface of the base cured layer is in the range of 1.0 to 5.0 nm.
  • the measurement by the DFM method is preferably performed under the condition of an observation area of 5 ⁇ m square, 256 ⁇ 256 measurement points, and the measurement is preferably performed in a plurality of regions, and the average value is preferably obtained.
  • photopolymerization initiators examples include those shown in the following (a) to (d). These may be used alone or in combination of two or more.
  • xanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone and 2,4-diethylthioxanthone; thioxanthones; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether;
  • (C) ⁇ -diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;
  • photopolymerization initiators 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino
  • One or more mixed systems selected from the group of phenyl) -butan-1-ones It allows more active against a broad range of wavelengths of light is preferred because highly curable coating is obtained using.
  • the amount of the photopolymerization initiator used is an amount capable of sufficiently exhibiting the function as a photopolymerization initiator, and is preferably in a range in which precipitation of crystals and deterioration of physical properties of the coating film do not occur, and specifically, It is preferably used in the range of 0.05 to 20 parts by mass, particularly preferably in the range of 0.1 to 10 parts by mass, based on 100 parts by mass of the resin composition.
  • the resin composition of the present invention may further use various photosensitizers in combination with the photopolymerization initiator.
  • the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.
  • An ultraviolet absorber, a solvent, and the like are further added to the coating agent for a cured underlayer of the present invention, if necessary.
  • the ultraviolet absorber any of organic and inorganic ultraviolet absorbers can be used.
  • the organic ultraviolet absorber include 2- [4- ⁇ (2-hydroxy-3-dodecyloxypropyl) oxy ⁇ -2- Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- ⁇ (2-hydroxy-3-tridecyloxypropyl) oxy ⁇ -2-hydroxy Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like, 2- (2′-xanthencarboxy-5′-methylphenyl) benzotriazole, 2- ( 2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2-xanthencarboxy-4-dodecyloxy
  • examples of the inorganic ultraviolet absorber include metal oxide fine particles such as titanium oxide, zinc oxide, and cerium oxide.
  • a triazine-based ultraviolet absorber is particularly preferably used in terms of the intensity and wavelength of ultraviolet absorption, the difficulty of decomposition, and the difficulty of elution.
  • the solvent is not particularly limited as long as it has affinity for both the (meth) acrylic resin and the inorganic fine particles in the coating agent, and the following solvents can be mentioned.
  • Ether solvents such as ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, and tetrahydrofuran.
  • Alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 3-methyl-3-methoxybutanol;
  • Hydrocarbon solvents such as toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1800, Swazol 310, Isopar E, Isopar G, Exxon Naphtha 5, Exxon Naphtha 6, etc.
  • the thickness of the cured layer is preferably in the range of 1 to 20 ⁇ m, more preferably 2 to 15 ⁇ m, still more preferably 3 to 10 ⁇ m, and most preferably 4 to 10 ⁇ m.
  • the thickness is less than 1 ⁇ m, the thickness is insufficient to absorb the difference in the coefficient of linear expansion between the silicon oxide layer and the silicon oxide layer formed by the PE-CVD method.
  • the thickness exceeds 20 ⁇ m, cracks occur in the layer due to the stress caused by the curing shrinkage of the layer, or the base layer increases in temperature due to the difference in linear expansion coefficient between the base layer and the silicon oxide layer. Since the silicon oxide layer cooperates to suppress the expansion of the underlayer, the underlayer may have wavy marks.
  • the surface of the hardened underlayer immediately before the silicon oxide layer is laminated by the PE-CVD method. For example, a method of performing a plasma treatment on the substrate.
  • Plasma treatment refers to a process in which gas species and electrons imparted with high kinetic energy by plasma excitation collide with the surface of the underlying hardened layer, and activates the surface of the underlying hardened layer (expression of active groups due to chemical bonding or cleavage of the crosslinked structure). ) Or etching of a surface layer portion having a low crosslink density can be performed.
  • a high-frequency electromagnetic field 13.56 MHz or the like is applied to generate plasma.
  • the main control parameters of the plasma processing are gas type, gas pressure or flow rate (directly gas concentration near the substrate), applied power of high frequency electromagnetic field (hereinafter referred to as high frequency applied power), distance between electrodes, processing time, etc.
  • the processing intensity can be controlled as these parameters.
  • an inert gas such as argon, helium, krypton, or an active gas such as oxygen, nitrogen, water, or carbon dioxide, which may be taken into a processing target under a plasma excitation condition in a chemically bonded state.
  • an inert gas such as argon, helium, krypton, or an active gas such as oxygen, nitrogen, water, or carbon dioxide.
  • the gas flow rate, high-frequency applied power, and distance between the electrodes depend on the area of the substrate and the electrode, the volume of the vacuum chamber, the shape of the substrate, and the like, it is difficult to specify a suitable range in a straightforward manner.
  • the processing time is preferably in the range of about 1 to 20 minutes, more preferably 2 to 15 minutes, and still more preferably about 3 to 10 minutes.
  • the plasma processing can be performed by an apparatus other than the capacitive coupling type CVD apparatus using the parallel plate electrodes.
  • a high frequency electromagnetic field is generated by an electromagnetic coil disposed around a substrate, and plasma is generated around the substrate.
  • a method of using an inductively coupled CVD apparatus, mainly an inductively coupled plasma gun, to accelerate gas particles to which high energy is given by a plasma field by means of an injection pressure or an electromagnetic field to impinge on a substrate surface this type of large Pressure plasma method.
  • the polymer substrate with a hard coat layer according to the present invention is a PE-CVD method for satisfying three characteristics of extremely high abrasion resistance comparable to inorganic glass, boiling water (including adhesion), and heat resistance.
  • the constituent requirements of the silicon oxide layer according to the above include the thickness of the silicon oxide, mechanical properties (elastic modulus, hardness), high density related to the fine structure of the silicon oxide layer, and the like.
  • the silicon oxide layer on the underground hardened layer includes an initial dense layer and a high hardness layer in order from the underground hardened layer side. Further, the silicon oxide layer may include a bulk layer between the initial dense layer and the high hardness layer.
  • the silicon oxide layer in the present invention satisfies all of the following requirements (a 1 ) to (c 1 ) at a position of 0.04 ⁇ m in the thickness direction from the interface between the above-described cured underlayer and the silicon oxide layer, and It is preferable that the surface on the opposite side satisfies all of the following requirements (a 3 ) to (c 3 ).
  • X in the above (a 1 ) is preferably in the range of 1.94 to 1.98, and more preferably in the range of 1.95 to 1.97.
  • y is preferably in the range of 0.04 to 0.12, and more preferably in the range of 0.04 to 0.07.
  • z is preferably in the range of 0.11 to 0.30, and more preferably in the range of 0.12 to 0.20.
  • ( ⁇ 930 / ⁇ 1020 ) in the above (b 1 ) is preferably in the range of 0.12 to 0.20, and more preferably in the range of 0.13 to 0.19. It is preferable that the content be in the above-mentioned range, since after the durability test (high-temperature constant-humidity environment, heat cycle, xenon weather meter test), excellent adhesion to the substrate is exhibited.
  • ( ⁇ 1280 / ⁇ 1020 ) in the above (c 1 ) is preferably in the range of 0 to 0.004, and more preferably in the range of 0 to 0.003.
  • the above range is preferable because the boiling water performance is improved.
  • the reason why the boiling water performance is good in the above range is that the silicon oxide layer formed by the PE-CVD method contains a small amount of a Si—CH 3 group in the layer, thereby exhibiting appropriate flexibility, and It is presumed that the effect of suppressing stress concentration is exerted.
  • x in the above (a 3 ) is preferably in the range of 1.94 to 2.00, and more preferably in the range of 1.94 to 1.98.
  • y is preferably in the range of 0.05 to 0.14, more preferably in the range of 0.04 to 0.13.
  • z is preferably in the range of 0.20 to 0.45, and more preferably in the range of 0.21 to 0.40.
  • ( ⁇ 930 / ⁇ 1020 ) in the above (b 3 ) is preferably in the range of 0.18 to 0.25, and more preferably in the range of 0.19 to 0.25. It is preferable for it to be in the above-mentioned range because excellent heat resistance (heat resistance test at high temperature) is exhibited.
  • ( ⁇ 1280 / ⁇ 1020 ) in the above (c 3 ) is preferably in the range of 0.002 to 0.015, and more preferably in the range of 0.002 to 0.010.
  • the above range is preferable because excellent heat resistance and excellent wear resistance and hardness can both be achieved.
  • y in the above (a 3 ) may be larger than y in the (a 1 ) by 0.02 or more, 0.03 or more, or 0.05 or more, and 0.10 or less, 0.08 or less, 0 It may be as large as 0.06 or less, or 0.04 or less.
  • z in (a 3 ) may be larger than z in (a 1 ) by 0.05 or more, 0.07 or more, 0.10 or more, 0.15 or more, and may be 0.25 or less, 0.20 or more. Hereinafter, it may be larger in the range of 0.15 or less, or 0.10 or less. It is preferable to form the silicon oxide layer at a gradient in such a manner, because the silicon oxide layer exhibits excellent wear resistance and also has heat resistance and durability.
  • the absolute value of the difference between x in (a 3 ) and x in (a 1 ) may be in the range of 0.05, 0.03, 0.02, or 0.01.
  • the ratio of the above (b 3 ) may be larger than the ratio of the above (b 1 ) by 0.05 or more, 0.07 or more, or 0.09 or more, and is 0.15 or less, 0.10 or less, and 0 or less. It may be larger in the range of 0.08 or less, 0.06 or less, or 0.04 or less.
  • the ratio of the above (c 3 ) may be larger than the ratio of the above (c 1 ) by 0.001 or more, 0.003 or more, or 0.005 or more, and 0.010 or less, 0.007 or less, and 0 or less. It may be larger in the range of 0.005 or less, or 0.003 or less.
  • the thickness of the silicon oxide layer in the present invention may be 0.1 ⁇ m or more, 0.2 ⁇ m or more, 0.3 ⁇ m or more, 1.0 ⁇ m or more, 3.0 ⁇ m or more, 5.0 ⁇ m or more, or 7.0 ⁇ m or more, and 9 ⁇ m or more. Hereinafter, it may be 8.5 ⁇ m or less, 8.0 ⁇ m or less, 6.0 ⁇ m or less, or 3.0 ⁇ m or less.
  • the range of the thickness may be 0.1 ⁇ m to 9 ⁇ m, 0.2 ⁇ m to 9 ⁇ m, or 0.3 ⁇ m to 9 ⁇ m.
  • the silicon oxide layer When the silicon oxide layer is thick, the silicon oxide layer has the following (a 2 ) to (c) at a position 2.0 ⁇ m in the thickness direction from the interface between the hardened underlayer and the silicon oxide layer. It is preferable to satisfy all the requirements of 2 ).
  • (A 2 ) When the chemical composition is represented by SiO x C y H z , x is in the range of 1.81 to 1.90, y is in the range of 0.15 to 0.32, and z is In the range of 0.45 to 0.90, (B 2) Infrared absorbance ratio of the wave number 930 cm -1 and 1020cm -1 ( ⁇ 930 / ⁇ 1020 ) may be in the range of 0.21 to 0.36, (C 2) Infrared absorbance ratio of the wave number 1280 cm -1 and 1020cm -1 ( ⁇ 1280 / ⁇ 1020 ) may be in the range of 0.010 to 0.040.
  • X in the above (a 2 ) is preferably in the range of 1.82 to 1.90, and more preferably in the range of 1.85 to 1.90.
  • y is preferably in the range of 0.16 to 0.30, and more preferably in the range of 0.17 to 0.29.
  • z is preferably in the range of 0.45 to 0.80, and more preferably in the range of 0.45 to 0.77.
  • the silicon oxide layer has a moderately dense silicon oxide layer (hereinafter sometimes referred to as a bulk layer), and has a linear expansion of each layer during a heat resistance test.
  • the compressive / tensile stress between the layers due to the difference in the ratio can be appropriately absorbed, the adhesion between the layers is reduced during the environmental tests such as a heat resistance test and a boiling water immersion test, and the coating layer is hardly cracked. .
  • the amount of the reactive functional group in the silicon oxide layer can be suppressed within an allowable range, cracks occur, the adhesion decreases, and the appearance changes (white turbidity) due to the reaction of the reactive functional group during the weather resistance test. Are less likely to occur.
  • ( ⁇ 930 / ⁇ 1020 ) in the above (b 2 ) is preferably in the range of 0.23 to 0.32, and more preferably in the range of 0.25 to 0.30. It is preferable for it to be in the above-mentioned range because excellent heat resistance (heat resistance test at high temperature) is exhibited.
  • ( ⁇ 1280 / ⁇ 1020 ) in the above (c 2 ) is preferably in the range of 0.012 to 0.030, and more preferably in the range of 0.012 to 0.020.
  • the denseness of the formed silicon oxide layer is moderate, so that the compressive / tensile stress between the layers can be appropriately absorbed during an environmental test such as a heat resistance test or a boiling water impregnation test. It is preferable because the silicon oxide layer hardly deforms or breaks during the indentation test to leave indentation marks.
  • a gradient layer in which the change in the values of the chemical composition (x, y, and z) and the infrared absorbance ratio ( ⁇ 930 / ⁇ 1020 , and / or ⁇ 1280 / ⁇ 1020 ) is gradient.
  • the presence of the gradient layer between the initial dense layer and the bulk layer makes it possible to appropriately absorb the stress at each interlayer interface during a heat resistance test or a weather resistance test, and is preferable because durability is improved. .
  • a portion (bulk layer) of the silicon oxide layer that satisfies all the requirements of (a 2 ) to (c 2 ) and a portion of the silicon oxide layer that satisfies all the requirements of (a 3 ) to (c 3 ) (The change in the chemical composition (x, y, and z) and the value of the infrared absorption ratio ( ⁇ 930 / ⁇ 1020 , and / or ⁇ 1280 / ⁇ 1020 ) between the high hardness layers)
  • the presence of the gradient layer between the bulk layer and the high-hardness layer makes it possible to appropriately absorb stress at each interlayer interface during a heat resistance test or a weather resistance test, and is preferable because durability is improved. .
  • the thickness of the portion satisfying all the requirements (a 1 ) to (c 1 ) is preferably from 0.04 ⁇ m to 0.4 ⁇ m, more preferably from 0.04 ⁇ m to 0.2 ⁇ m, and more preferably from 0.04 ⁇ m to 0.2 ⁇ m.
  • the thickness is more preferably from 0.4 ⁇ m to 0.10 ⁇ m, and most preferably from 0.04 ⁇ m to 0.07 ⁇ m. With the above thickness, it is preferable to form a layer having sufficient adhesion to the cured underlayer and hardly causing cracks in the silicon oxide layer in a heat test.
  • the thickness of the portion satisfying all the requirements (a 2 ) to (c 2 ) is preferably 1.5 ⁇ m to 8.5 ⁇ m, more preferably 2.0 ⁇ m to 7.0 ⁇ m, and 3. More preferably, it is 0 ⁇ m to 6.7 ⁇ m.
  • the difference in (linear) expansion (rate) between the layers during a heat resistance test, a boiling water test, or the like is absorbed to improve the adhesion, and the component is hardly cracked. This is preferable because cracks are hardly formed in the structure.
  • the thickness of the portion satisfying all the above requirements (a 3 ) to (c 3 ) is preferably 0.1 ⁇ m to 1.4 ⁇ m on the surface, and 0.2 ⁇ m to 1.2 ⁇ m. More preferably, it is present on the surface at 0.3 ⁇ m to 1.1 ⁇ m. The above thickness is preferable because the wear resistance, heat resistance, and durability are improved.
  • the thickness of the silicon oxide layer in the present invention is 2.5 ⁇ m or less, for example, 0.1 ⁇ m to 2.5 ⁇ m, 0.1 ⁇ m to 2.4 ⁇ m, 0.1 to 2.3 ⁇ m, 0.1 to 2.3 ⁇ m. It may be 2.2 ⁇ m, 0.1 to 2.1 ⁇ m, or 0.1 to 2.0 ⁇ m.
  • the presence of the gradient layer between the initial dense layer and the high hardness layer makes it possible to absorb a certain amount of stress at each interlayer interface during a heat resistance test or a weather resistance test, and is preferable because durability is improved. .
  • the infrared absorbance at a wave number of 930 cm ⁇ 1 reflects the relative content of Si—OH groups, and the larger the value, the more the Si—OH groups are generated by oxidative decomposition of the raw material organosilicon compound during PE-CVD film formation.
  • the dehydration-condensation reaction and the progress of crosslinking to form a three-dimensional network structure of Si—O—Si are in an insufficient state, indicating that the thermal stability is relatively low.
  • the infrared absorbance at a wave number of 1020 cm -1 indicates the degree of formation of a three-dimensional network structure of Si-O-Si
  • the infrared absorbance at a wave number of 1280 cm -1 indicates that Si-CH 3 in a silicon oxide layer by PE-CVD. Reflects the relative content of groups.
  • the absorbance it is preferable to measure the absorption spectrum by the ATR method in the wavenumber region of 650 cm -1 to 1500 cm -1 on the surface of the polymer substrate with the hard coat layer on which the PE-CVD layer is formed.
  • infrared absorbance alpha K for each wave number is from the 650 cm -1 the value of the absorption spectrum of 1500 cm -1, respectively performs a correction to subtract the following baseline alpha B.
  • the silicon oxide layer formed by the PE-CVD method preferably has a maximum indentation depth of 140 nm or less in nanoindentation measurement under a maximum test load of 1 mN in order to obtain good Taber abrasion.
  • the maximum indentation depth is larger than 140 nm, the indentation depth of the silicon oxide layer surface by the abrasion particles relatively increases upon contact wear between the silicon oxide layer and the abrasion particles by the PE-CVD method, As a result, the depth of the scratches (concave portions generated by abrasion) is increased, and the destruction of the layer proceeds.
  • the maximum indentation depth by nanoindentation measurement under these conditions is more preferably 130 nm or less, and still more preferably 120 nm or less.
  • the maximum indentation depth of the surface of a commercially available silicon wafer is measured under these conditions, the value is around 55 nm, and when the surface of a commercially available fused quartz plate is measured, the value is around 75 to 80 nm.
  • the silicon oxide layer formed by the PE-CVD method is preferably a layer having a high hardness in order to obtain excellent Taber abrasion resistance. It is more preferable that the indentation hardness by nanoindentation measurement under a test load of 1 mN is 4.5 GPa or more. This is because when the hardness of the layer is high, the size of damage due to abrasion particles or the like becomes small.
  • the measurement of nanoindentation is preferably performed by using Elionix ultra-fine indentation hardness tester ENT-2100.
  • the indentation hardness by nanoindentation measurement under these conditions is more preferably 5.0 GPa or more, further preferably 5.2 GPa or more, and most preferably 6.0 GPa or more.
  • the silicon oxide layer formed by the PE-CVD method preferably has a dense fine structure in order to obtain excellent Taber abrasion.
  • the surface preferably has a surface roughness (Ra) of 5.0 nm or less measured under a dynamic force mode (DFM) of a scanning probe microscope under a 5 ⁇ m square observation condition.
  • DFM dynamic force mode
  • the DFM method is a measurement method using a scanning probe microscope that performs measurement in a vibration mode (dynamic force mode). Since the measurement surface is less affected by abrasion on the sample surface and the surface charge, the PE is often electrically insulating. -Effective for surface observation of a silicon oxide layer by a CVD method.
  • the silicon oxide layer formed by the PE-CVD method is vapor-phase-grown into fine particles of nanometer size, and the layers are formed so that they are stacked on each other.
  • the surface roughness and the surface area ratio of the layer surface depend on the PE-CVD film formation conditions, a silicon oxide layer having a surface roughness of 5.0 nm or less measured under a 5 ⁇ m square observation condition has a high layer density, It is structurally stable and shows strong resistance to surface wear. If the surface roughness is more than 5.0 nm, the particle size of the vapor phase growth is large, the denseness of the layer is low, and the structure is relatively sparse, so that the resistance to surface wear is low.
  • the surface roughness is more preferably 4.0 nm or less, and still more preferably 3.0 nm or less.
  • the measurement of the surface roughness (Ra) and the surface area ratio by the DFM method may differ depending on the measuring device, the cantilever, and the measuring conditions. Therefore, preferably, the device is a scanning probe microscope manufactured by Hitachi High-Tech Science Corporation.
  • the SPI 3800N and the cantilever are preferably measured under the conditions of NSG10 manufactured by NT-MDT, an observation area of 5 ⁇ m square, and the number of measurement points is 256 ⁇ 256.
  • the measurement is preferably performed in a plurality of regions and an average value thereof is preferably obtained. In the present invention, the measurement is performed at 10 or more points.
  • the silicon oxide layer formed by the PE-CVD method is more preferably formed at a low initial deposition rate (nm / sec) from the beginning of the deposition, for example, 30 seconds or 60 seconds after the start of the deposition.
  • the particle size of the silicon oxide layer formed by PE-CVD (at the time of initial deposition) formed in the vicinity of the interface with the hardened base layer can be reduced, thereby increasing the density.
  • a layer is obtained.
  • This deposition rate is preferably 1 nm / sec or less, more preferably 0.8 nm / sec or less, and still more preferably 0.6 nm / sec or less.
  • the time for depositing a layer at a low deposition rate is preferably in the range of 30 to 180 seconds after the start of deposition. This is because the denseness of the layer is high and the modulus of elasticity is high, so that as the deposition time increases, that is, as the thickness of the layer increases, the interfacial stress with the hardened base layer increases and the adhesion may decrease. It is.
  • the deposition time is more preferably in the range from 30 to 120 seconds, even more preferably in the range from 30 to 90 seconds.
  • the deposition rate By increasing the deposition rate, the productivity of forming a silicon oxide layer can be increased.
  • the large deposition rate in this case may be, for example, 2 nm / sec or more, 3 nm / sec or more, 4 nm / sec or more, 5 nm / sec or more, 7 nm / sec or more, or 10 nm / sec or more.
  • Switching from a lower deposition rate to a higher deposition rate can be accomplished by changing the deposition rate in two or more steps, stepwise or continuously, at a lower deposition rate. It is preferred to maintain continuity between the layer and the layer obtained at a high deposition rate and to suppress delamination.
  • Plasma generation method used for exciting the decomposition and condensation reaction of the raw material organosilicon compound, for example, capacitive coupling in which plasma is generated in a space within a parallel plate using opposed parallel plate electrodes.
  • Method using an inductively-coupled plasma device that generates plasma in the space inside the coil using an electromagnetic coil, and a gas that is given high energy by a plasma field mainly using an inductively-coupled plasma gun An apparatus (including an atmospheric pressure plasma apparatus, which is one kind of the apparatus), in which particles are accelerated by a jet pressure or an electromagnetic field to collide with a substrate surface, is included.
  • a method using a capacitively-coupled plasma apparatus excellent in uniform control of plasma density and stability is preferable.
  • a device having a cooling mechanism such as a pipe of water or other refrigerant inside the electrode, in which the electrode holding and fixing the substrate also functions as a heat sink is preferable, and the polymer substrate is brought into planar contact with one of the parallel plate electrodes.
  • the electrode having the heat sink function is preliminarily formed into a shape conforming to the substrate shape so that the polymer substrate can be brought into close contact with the polymer substrate. It is preferably processed. It is also preferable to process and prepare metal attachments of various shapes according to the shape of each substrate so as to be adaptable to various types of substrates, and to make them detachable according to the substrate shape.
  • the metal used for the electrode be a material that is not easily affected by corrosion or deterioration and erosion due to plasma, and examples thereof include stainless steel (SUS) and aluminum.
  • a capacitively coupled plasma device use is made of either an external electrode system in which the high-frequency electrode is installed outside the vacuum chamber (reaction vessel) or an internal electrode system in which the high-frequency electrode is installed inside the vacuum chamber (reaction vessel). Can be.
  • a high-frequency power supply is used to supply high-frequency power, and the frequency may be any frequency specified as an industrial frequency band by the Radio Law, for example, 13.56 MHz, 27.12 MHz, 40.68 MHz, 85 MHz 2.45 GHz, 5.8 GHz, 22.125 GHz, etc., but 13.56 MHz can be used most generally.
  • the applied power in applying high-frequency power (hereinafter referred to as high-frequency applied power) varies depending on the type of raw material used, the size of the PE-CVD apparatus (size of substrate), and the like, but is generally about 50 to 10,000 W. However, many power supplies that are commercially available and can be used for general purposes are 5,000 W or less, and it is preferable to control the input power to 5000 W or less.
  • the high-frequency applied power is continuously applied, but if necessary, a partly intermittent pulsed power may be applied.
  • the degree of vacuum of the vacuum tank (reaction vessel) is preferably 10 ⁇ 2 Pa or less, more preferably 10 ⁇ 3 Pa or less, as the ultimate degree of vacuum exhaustion of the vacuum vessel (reaction vessel) before each step. It is.
  • the degree of vacuum at the time of forming a silicon oxide layer by PE-CVD or at the time of plasma treatment is preferably 20 Pa or less, more preferably 10 Pa or less, from the viewpoint of maintaining stable plasma and ensuring uniformity. It is generally preferred to be 1 ⁇ 10 ⁇ 2 Pa or more.
  • an organic silicon compound containing a carbon atom As the organic silicon compound as a raw material in forming the silicon oxide layer by the PE-CVD method, an organic silicon compound containing a carbon atom, an organic silicon compound containing a carbon atom and an oxygen atom or a nitrogen atom, and the like are preferable.
  • organosilicon compounds can be used alone or in combination of two or more. Further, the purpose of controlling decomposition, condensation to promote, also like the chemical composition of the silicon oxide layer formed (e.g. represented by SiO x C y H z, etc.) in a plasma vapor space of the organic silicon compound
  • gases such as oxygen, nitrogen, argon, helium, and hydrogen (hereinafter, these are referred to as carrier gases) are preferably used in combination.
  • carrier gases such as oxygen, nitrogen, argon, helium, and hydrogen
  • the organosilicon compound and the carrier gas may be premixed and supplied to a vacuum reactor of a plasma polymerization apparatus, or may be separately supplied to the vacuum reactor and mixed with each other in the vacuum reactor. You can also.
  • the ratio of oxygen to the organic silicon compound depends on the type of the organic silicon compound used and the desired chemical composition of the silicon oxide layer, film quality, etc., and cannot be specified unconditionally. It is appropriately selected from a range of about 5 to 500 times by volume, more preferably 10 to 100 times by volume of the vapor of the silicon compound.
  • the gas flow rate during the film formation, the high-frequency applied power, and the electrode-to-electrode distance also depend on the area of the substrate or electrode, the volume of the vacuum chamber, the shape of the substrate, etc., it is difficult to specify a suitable range.
  • the total flow rate of the gas including the organic silicon compound as the raw material and the carrier gas is generally in the range of about 1000 to 5000 sccm
  • the high frequency applied power is about 2 to 7 KW
  • the control is performed in the range of 3 to 5 KW
  • the distance between the electrodes is controlled in the range of about 80 to 300 mm.
  • the film formation time of the silicon oxide layer is preferably in the range of about 1 to 30 minutes, more preferably about 2 to 20 minutes, and still more preferably about 3 to 10 minutes. Note that, if necessary, the film formation can be performed in a time-divided manner.Also, even if the film formation is divided and performed in a plurality of vacuum tanks that are separated from each other by partition walls and can be interconnected by an in-line method or the like. good.
  • the flow rate of the organic silicon compound as the raw material, the carrier gas, and / or the high-frequency applied power and frequency are preferably changed with time, if necessary.
  • Each flow rate, high frequency applied power, frequency and the like may be changed alone or simultaneously.
  • FIG. 1 shows an example of a capacitively coupled CVD apparatus that can be suitably used for forming the polymer substrate with a hard coat layer according to the present invention.
  • the first electrode 10, the second electrode 20, the substrate 30 to be processed, and the introduction head 40 are arranged vertically, but they may be arranged horizontally.
  • a first electrode (cathode electrode) 10 and a second electrode (anode electrode) 20 are arranged inside the vacuum vessel 1 so as to face each other.
  • a polymer substrate 30 which is a substrate to be processed is arranged and supported by the holder 12.
  • the interior of the vacuum vessel 1 is evacuated by a vacuum pump 5 from an exhaust port 4, and while introducing a reaction gas 7 from the outside into the vacuum vessel 1 through an introduction head 40, plasma of the reaction gas is supplied to a first electrode (cathode).
  • An electrode (electrode) 10 and a second electrode (anode electrode) 20 are formed.
  • the first electrode (cathode electrode) 10 is connected to the power supply 2 via the matching box 3. It is insulated from the vacuum vessel 1 by an insulating seal 6. Although not shown in detail, a cooling medium 6A is circulated in the first electrode (cathode electrode) 10, and the cooling heat is transmitted through the interface between the first electrode 10 and the polymer substrate 30, so that the polymer substrate The cooling of 30 is achieved. Further, a shield member 14 is provided on the outer peripheral surface of the first electrode (cathode electrode) 10 except for the surface facing the second electrode (anode electrode) 20 at a slight interval. The second electrode (anode electrode) 20 is grounded.
  • a box-shaped reaction gas introduction head 40 is provided between the polymer substrate 30 to be processed and the second electrode (anode electrode) 20.
  • the introduction head 40 has a large number of gas ejection holes 40A on the wall surface on the side opposite to the first electrode (cathode electrode) 10, and the reactive gas 7
  • the liquid is introduced into the introduction head 40 through the inlet 40B.
  • the reaction gas 7 introduced into the introduction head 40 is ejected from the ejection hole 40A toward the first electrode (cathode electrode) 10 side, that is, toward the polymer substrate 30 held on the surface of the first electrode (cathode electrode) 10. It is configured to:
  • the introduction head 40 is preferably in the shape of a flat box, but the specifications are not limited to those shown in the drawings. Depending on the shape and dimensions of the polymer substrate 30 to be processed, the shape of the box and the shape and size of the ejection hole 40A are determined. , Formation density, spacing, distribution, etc. can be freely adjusted. However, in many cases, the ejection hole 40A is preferably a circle having a diameter of about 2 to 7 mm, and the interval (pitch) between the holes is preferably about 4 to 20 mm.
  • the polymer substrate has a two-dimensional or three-dimensional three-dimensional shape or a curved surface shape
  • FIG. 2 shows another example of a capacitively coupled CVD apparatus which can be suitably used for forming a polymer substrate with a hard coat layer according to the present invention.
  • the polymer substrate 31 of the substrate to be processed has a curved shape. It shows a specification example of a device suitable for the case where there is.
  • the first electrode (cathode electrode) 10, the second electrode (anode electrode) 20, and the introduction head 41 have the same curved shape as the curved shape of the polymer substrate 31.
  • the reaction gas is placed in the plasma reaction space sandwiched between the polymer substrate 30 on the first electrode (cathode electrode) 10 and the introduction head 41 on the second electrode (anode electrode) 20. 7 is preferable in improving the uniformity of the density distribution and the distribution of high-frequency power (spatial electric field, spatial current).
  • the polymer substrate with a hard coat layer of the present invention if necessary, it is further laminated on the PE-CVD silicon oxide layer formed on the surface layer on one or both sides, the conductive layer, and the infrared absorption / reflection layer, and Functional layers such as an anti-static layer and an anti-static layer may be laminated.
  • the stain prevention layer is a layer having a function of suppressing the adhesion of fingerprints and stains to the silicon oxide layer by the PE-CVD method and the generation of water scale due to long-term use in an outdoor environment. It is a layer having an effect of increasing water-repellency, oil-repellency, hydrophilicity, lipophilicity and the like for a long period of time. These layers are preferably formed as a thin film having a thickness of several nm to several hundreds of nm. Specifically, for example, a water-repellent and / or oil-repellent layer formed of a layer obtained by decomposing and condensing a silicon compound having an alkyl fluorine group.
  • a titanium oxide layer, a zinc oxide layer, a niobium oxide layer, a hydrophilic and / or lipophilic layer by a cerium oxide layer, and the like is a layer having a photocatalytic function that acts as an oxidation-reduction catalyst when excited by ultraviolet light or light in the visible wavelength range, it can be used in sunlight or rain in an outdoor environment. By the combined action, a self-cleaning effect of decomposing dirt attached to the outermost surface and washing it off is obtained, which is preferable.
  • the antistatic layer layer having electrical conductivity
  • examples of the antistatic layer include a transparent conductive layer (ITO, IZO, etc.) made of a metal oxide containing indium oxide, tin oxide, zinc oxide, or the like as a main component, a metal, a metal oxide,
  • a transparent conductive layer formed by dispersing a conductive material such as a carbon-based material in a layer made of a hydrolyzed condensate of an organic silicon compound, or the like can be given.
  • the transparent conductive layer As the conductive layer, the transparent conductive layer, a layer formed by printing a conductive paste obtained by dispersing fine metal particles having excellent conductivity such as silver and copper in a resin binder, a metal thin plate or a metal foil may be used.
  • the antistatic layer and the conductive layer do not necessarily need to be formed on the outermost surface, but are formed on a polymer substrate, an adhesive layer, a cured underlayer, or the like.
  • a hardened layer and / or a silicon oxide layer formed by a PE-CVD method may be stacked.
  • the conductive layer may be integrally formed with the polymer substrate by a method such as insert molding or in-mold transfer at the time of molding the polymer substrate.
  • the polymer substrate with a hard coat layer of the present invention has an object of, for example, relaxing the intrinsic strain and further promoting cross-linking and curing of the laminated layers after the silicon oxide layer is laminated by the PE-CVD method, if necessary. Then, if necessary, a thermal annealing treatment may be performed.
  • the annealing treatment may be performed under vacuum pressure or normal pressure, but is preferably performed at a temperature in the range of about 60 to 130 ° C.
  • the processing time depends on the processing temperature, but is preferably about 10 minutes to 48 hours.
  • the hard coat layer in the Taber abrasion test at a wear wheel CS-10F, a load of 4.9 N and a test rotation speed of 1,000 rotations in accordance with the test standard of ASTM D1044 is used for the purpose described above.
  • a silicon oxide layer is formed on one or both surfaces using a PE-CVD method capable of forming a hard coat layer having a hardness close to that of an inorganic glass so that the haze value increase ( ⁇ H) of the laminated surface is 2% or less.
  • the haze value (haze value) of the polymer substrate with a hard coat layer of the present invention at the initial stage (before the abrasion resistance test, the environmental resistance test, etc. is performed) can be used for applications requiring high visibility such as automobile windows.
  • the content is preferably 1.0% or less, more preferably 0.8% or less, and still more preferably 0.6% or less. If the haze value exceeds 1.0%, the fluoroscopic image becomes unclear, which may cause a problem in driving safety. (In some countries, the fogging value is 1. 0% or less may be required).
  • the visible light transmittance of the polymer substrate with a hard coat layer of the present invention is preferably set to 70.0% or more when used for applications requiring high visibility such as automobile windows.
  • the visible light transmittance is defined as the total light transmittance in the visible wavelength range with respect to the C light source or the D65 light source, and although it depends on the application, it is generally more preferably 75% or more, still more preferably 80% or more, and most preferably. 85% or more.
  • the polymer substrate with a hard coat layer of the present invention may be colored as required, and may be green, gray, or other various colors. These colorings generally depend on the mixing of appropriate amounts of pigments, dyes, etc., but may be mixed in a polymer substrate or may be mixed in a coating layer laminated on the polymer substrate.
  • the polymer substrate with a hard coat layer of the present invention preferably has at least a predetermined performance in an accelerated weather resistance test with respect to resistance to long-term use in an outdoor environment (ultraviolet light, temperature change, humidity change, etc.). Specifically, for example, using a Super Xenon Weather Meter SX-75 manufactured by Suga Test Instruments Co., Ltd., a UV irradiation intensity of 180 W / m 2 , a black panel temperature of 63 ° C., and a rainfall condition of 8000 hours under rainfall conditions of 18 minutes out of 120 minutes When an exposure test is performed, no reduction in appearance or adhesion is observed, and more preferably 10,000 hours or more.
  • ⁇ Wear resistance of polymer substrate with hard coat layer> Regarding the abrasion resistance equivalent to inorganic glass, for example, referring to standards such as the North American safety standard FMVSS205 and the European safety standard ECE R43, the abrasion resistance of windows used in parts that require visibility during operation The property requirement is a haze value increase ( ⁇ H) of less than 2% to 2% or less according to a Taber abrasion test at 1000 revolutions specified in ASTM D1044.
  • ⁇ Boiling water resistance and adhesion of polymer substrate with hard coat layer The polymer substrate with the hard coat layer is immersed in boiling water at 100 ° C., kept for 3 hours, taken out of the boiling water, removed from adhering water, left for 2 hours at room temperature environment, and then laid in a JIS K5400 compliant grid board.
  • An adhesion test is performed by the eye tape method. In the cross-cut tape test, a square having 10 ⁇ 10 cuts was formed into a cross-cut shape at 1 mm intervals with a cutter knife, and then a tape having a predetermined adhesive strength (for example, Nichiban Cellotape (trademark)) was attached and fixed. It is done in a form to be peeled off later.
  • a predetermined adhesive strength for example, Nichiban Cellotape (trademark)
  • Adhesion results immediately after the cross-cut tape test (the state of peeling of the layers and the appearance of the layer) are referred to as “initial results”, and the results after 7 days from the cross-cut tape test are performed are “time-lapse results”. However, only when the “time result” is good, it is determined that the adhesion performance and its reliability are good.
  • X-ray electron spectroscopy (XPS) measurement of the surface of the silicon oxide layer was performed to measure the chemical composition of the surface of the structure.
  • the calibration curve was created by performing XPS measurement of dimethyl silicone rubber.
  • the surface of the silicon oxide layer was polished with an abrasive using fine diamond particles on the polymer substrate sample with a hard coat layer, where the silicon oxide layer was partially peeled off by applying a compressive stress in the bending test, and the base was cured. Samples polished from the interface with the layer to 2 ⁇ m and 0.04 ⁇ m were prepared, and XPS measurement was performed to determine the chemical composition of the silicon oxide layer.
  • the thickness of the silicon oxide layer was determined by performing step contact measurement, optical measurement (focal length measurement), cross-sectional SEM measurement, refractive index measurement, interference film thickness measurement, and the like.
  • ATR-IR measurement was performed on the surface of the polymer substrate sample with the hard coat layer using a zirconium sensor, and the infrared absorbance ratio of the silicon oxide layer was measured. Further, the surface of the silicon oxide layer was polished with an abrasive using diamond fine particles, and a sample was polished to 2 ⁇ m and 0.04 ⁇ m from the interface with the underlying hardened layer, and ATR-IR measurement was similarly performed. .
  • the maximum load is 1 mN
  • the load step is 4 ⁇ N
  • the number of steps is 250
  • the load time is using a triangular pyramid indenter with an apex angle of 65 degrees (edge interval 115 degrees) using an ultra-fine indentation hardness tester ENT-2100 manufactured by Elionix Inc.
  • a load unloading curve was measured under the conditions of 20 sec, unloading time of 20 sec, and maximum load holding time of 0.4 sec, and the calculation was performed according to ISO 14577-1 2002-10-01 Part 1 (calculation by software in the apparatus).
  • the tip of the triangular pyramid indenter may change due to processing variations or wear due to use, causing variations in measurement values or uncertainty. It is preferred to do either.
  • the confirmation work was performed by measuring a commercially available silicon wafer under the above test conditions and confirming that the maximum indentation depth was within the range of 55 ⁇ 3 nm. If the depth was outside this range, replace the triangular pyramid indenter with a new one. (In the case of measurement using the company's testing machine ENT-1100, use this method).
  • the correction work can be performed based on the measurement of the fused quartz plate as a standard sample and the built-in software of the tester. (Due to the built-in software, this method can be used only for measurement using the company's tester ENT-2100.) Is). This test result is used as one evaluation criterion of wear resistance.
  • the surface roughness (average surface roughness, Ra) is a value obtained by averaging the absolute value of the deviation of the height (Z coordinate) from the reference surface to the specified surface.
  • the reference plane is a plane having the average value of the Z coordinates of all the measurement points
  • the designated plane is a plane connecting the Z coordinates of all the measurement points (a unit plane is a triangle formed by connecting the three closest points).
  • the surface area ratio is a ratio of the area of the designated surface (measurement surface) to the area of the reference surface (a flat plane having a constant Z coordinate).
  • the thickness of each layer is preferably measured by a known optical interference method based on an optical interference pattern appearing in a transmission spectrum or a reflection spectrum measured in a wavelength range of, for example, 450 to 650 nm and a refractive index of each layer.
  • a known optical interference method based on an optical interference pattern appearing in a transmission spectrum or a reflection spectrum measured in a wavelength range of, for example, 450 to 650 nm and a refractive index of each layer.
  • the difference in the refractive index of each layer is small, or when the optical interference pattern becomes unclear due to disturbances (irregularities) at the layer interface and measurement is difficult, as an alternative, hard coating using a scanning electron microscope is used.
  • the measurement may be performed based on observation of a cross section of the polymer substrate with a layer. In any case, the measurement is performed at five or more points in different places, and the average value is obtained.
  • the refractive index of each layer is measured with an Abbe refractometer or the like
  • ⁇ Taber abrasion test> As one evaluation criterion of wear resistance, the surface of a polymer substrate with a hard coat layer having a silicon oxide layer by a PE-CVD method was evaluated using a CS-10F abrasion wheel manufactured by Taber Co., Ltd. After polishing the surface of the 25-wheel abrasion wheel with 11 grinding stones, a 1000-rotation Taber abrasion test was performed with a load of 500 g, and the change ( ⁇ H) of the haze value before and after the Taber abrasion test was measured and evaluated (ASTM). D1044).
  • the measurement was performed on three test pieces having the same specifications, and the average value was used as the performance value of the sample.
  • the wear wheel used in the test had a change in haze value ( ⁇ H) of 0.6 to 1.0% when a commercially available float glass (sheet glass) was subjected to a Taber abrasion test at 1,000 revolutions in the same manner as described above. After confirming that it is within the range, the test shall be performed, and worn wheels that fall outside the range shall not be used for the test.
  • a test piece of a polymer substrate with a hard coat layer cut into a size of 60 mm ⁇ 120 mm is immersed in boiling water at 100 ° C., kept for 3 hours, taken out of the boiling water, removed adhering water, and left at room temperature for 2 hours. After the standing, the appearance of the surface of the polymer substrate with the hard coat layer having the silicon oxide layer and the test of the adhesion are performed by the PE-CVD method.
  • a test is performed by a grid tape method in accordance with JIS K5400, and a square having 10 ⁇ 10 cuts at 1 mm intervals is formed in a grid with a cutter knife, and then a tape having a predetermined adhesive strength (For example, Nichiban Cellotape (trademark)), which is adhered and fixed, and then peeled off.
  • a tape having a predetermined adhesive strength For example, Nichiban Cellotape (trademark)
  • test result The result after the elapse of 7 days from the execution of the “adhesion” test is referred to as “timed result”.
  • the results of the aging were judged to be the same as those immediately after the test (A), and the hard coat layer was partly peeled off from the substrate mainly from the part damaged by a cutter knife for evaluation of adhesion.
  • the case where the state has been performed is regarded as defective (D).
  • D defective
  • the polymer substrate with a hard coat layer of the present invention it is a requirement that “appearance”, “adhesion”, and “time-lapse result” are all good.
  • the size of the test piece can be other than the above.
  • a test piece of a polymer substrate with a hard coat layer cut into a size of 60 mm ⁇ 120 mm is kept at 110 ° C. or 130 ° C. in a thermostat, and after 1000 hours, with a hard coat layer having a silicon oxide layer by PE-CVD.
  • the appearance and adhesion of the surface of the polymer substrate were evaluated.
  • the result after the elapse of 7 days since the test was performed is referred to as “timed result” in the same manner as the boiling water resistance.
  • ⁇ Accelerated weather resistance> Using a Super Xenon Weather Meter SX-75 manufactured by Suga Test Instruments Co., Ltd., an exposure test was performed for 2000, 4000, and 8000 hours under the conditions of a UV irradiation intensity of 180 W / m 2 , a black panel temperature of 63 ° C. and a rainfall of 18 minutes in 120 minutes, After taking out the test piece, the surface of the polymer substrate with a hard coat layer having a silicon oxide layer by PE-CVD method is gently rubbed and washed with a sponge impregnated with a neutral detergent, and then the appearance and adhesion, the color difference before and after the test. ( ⁇ E) was evaluated.
  • the “active ingredient” is a value obtained by dividing the theoretical yield (parts by weight) when all the methoxy groups of the silane monomer used have undergone the hydrolysis-condensation reaction by the actual yield (parts by weight) after the hydrolysis-condensation reaction, That is, it is calculated by the formula [theoretical yield (parts by weight) in the case where all methoxy groups of the silane monomer are subjected to hydrolysis / condensation reaction / the actual yield (parts by weight) after hydrolysis / condensation reaction].
  • Synthesis example 2 [Preparation example of vinyl polymer (a2)]
  • PTMS phenyltrimethoxysilane
  • DDMS dimethyldimethoxysilane
  • n-butyl acetate a reaction vessel similar to that of Synthesis Example 1, 20.1 parts of phenyltrimethoxysilane (PTMS), 24.4 parts of dimethyldimethoxysilane (DMDMS), and 107.7 parts of n-butyl acetate were charged, and nitrogen gas was introduced. The temperature was raised to 80 ° C. while stirring.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • CHMA cyclohexyl methacrylate
  • AA acrylic acid
  • MPTS 2-hydroxyethyl
  • HEMA methacrylate
  • TPEH tert-butylperoxy-2-ethylhexanoate
  • Example 1 Polycarbonate resin (Panelite L1250Z, Teijin Limited) was injected into an injection press molding apparatus to obtain a 4 mm thick, 600 mm square transparent polycarbonate resin plate.
  • the undercoat layer coating agent (P1) was dip-coated on both surfaces thereof, air-dried, and then irradiated with ultraviolet light of 2000 mJ / cm 2 from both surfaces using a high-pressure mercury lamp to obtain a film thickness of about 8 ⁇ m.
  • the undercoat layer coating agent (P1) was dip-coated on both surfaces thereof, air-dried, and then irradiated with ultraviolet light of 2000 mJ / cm 2 from both surfaces using a high-pressure mercury lamp to obtain a film thickness of about 8 ⁇ m.
  • a high-pressure mercury lamp was formed on both surfaces of a polycarbonate substrate.
  • a polycarbonate resin substrate having a size of 60 ⁇ 60 cm and a base cured layer formed on both sides thereof was brought into close contact with the electrode surface on the high-frequency power application side of the parallel plate electrode of the capacitively coupled PE-CVD apparatus shown in FIG. It was set in the state (30 in the figure) and evacuated for 1 hour. The ultimate vacuum pressure was 0.03 Pa.
  • an argon gas (purity of 99.9% or more) was introduced into the system at 1200 sccm, and a 13.56 MHz, 1.0 kW high frequency power was supplied to a parallel flat plate having a cooling pipe inside. A voltage was applied between the electrodes to generate plasma in the space between the parallel plate electrodes. In this state, high-frequency power was applied for a total of 200 seconds to perform a plasma treatment on one surface of the base cured layer.
  • D4H 1,3,5,7-tetramethylcyclotetrasiloxane
  • 300 sccm of oxygen purity of 99.9% or more
  • the system was introduced into the system through separate pipes attached thereto, and high-frequency power of 13.56 MHz and 1.5 KW was applied between the parallel plate electrodes via a matching box to generate plasma in the space between the parallel plate electrodes.
  • the average deposition rate from the start of the formation of the silicon oxide layer by the PE-CVD method to 30 seconds after the start was 0.8 nm / sec.
  • the D4H flow rate is continuously increased to 50 sccm and the oxygen flow rate to 1000 sccm for 60 seconds while maintaining the high-frequency power of 1.0 KW. Lowered.
  • the D4H flow rate is continuously reduced to 0 sccm in 30 seconds while maintaining the high-frequency power of 1.0 KW, and the high-frequency power is applied. Stopped.
  • the oxygen flow rate was fixed at 1000 sccm until the application of the high-frequency power was stopped.
  • the substrate on which the silicon oxide layer has been formed by the PE-CVD method is cooled on a parallel plate electrode for 5 minutes, and the inside of the apparatus is returned to the atmospheric pressure and taken out of the apparatus. A polymer substrate with a layer was obtained.
  • the thickness of the entire silicon oxide layer by PE-CVD is 5.8 ⁇ m, calculated by rounding off the second decimal place, the thickness of the initial dense layer is 0.05 ⁇ m, and the initial dense layer-bulk layer film quality is calculated.
  • the thickness of the layer (gradient layer) in the continuously changing portion is 0.2 ⁇ m
  • the thickness of the bulk layer is 4.2 ⁇ m
  • the thickness of the layer (gradient layer) in the bulk layer-hard layer is 0.4 ⁇ m.
  • the thickness of the high hardness layer was 0.9 ⁇ m.
  • Table 2 shows the performance evaluation results of the polymer substrate with the hard coat layer and the physical properties of each layer. Also in the following Examples and Comparative Examples, Tables 3 to 11 show the performance evaluation results of the polymer substrate with a hard coat layer obtained in each example and the physical properties of each layer, as in Example 1.
  • the physical property values of the underlying hardened layer in the table are physical property values immediately before the silicon oxide layer is formed by the PE-CVD method after the same layer is subjected to the plasma treatment.
  • Example 2 A polymer substrate with a hard coat layer was formed in the same manner as in Example 1, except that the conditions for forming the silicon oxide layer were changed to the conditions shown in Table 2 below.
  • the thickness of the silicon oxide layer obtained by the PE-CVD method was about 8.3 ⁇ m.
  • the maximum temperature of the substrate surface on the side where the silicon oxide layer was laminated by the PE-CVD method was about 115 ° C.
  • the thickness of each layer is shown in Table 3 below.
  • Example 3 A polymer substrate with a hard coat layer was formed in the same manner as in Example 1, except that the conditions for forming the silicon oxide layer were changed to the conditions shown in Table 2 below.
  • the thickness of the silicon oxide layer formed by the PE-CVD method was about 5.7 ⁇ m.
  • the maximum temperature of the substrate surface on the side where the silicon oxide layer was stacked by the PE-CVD method was about 110 ° C.
  • the thickness of each layer is shown in Table 3 below.
  • Example 4 A polymer substrate with a hard coat layer was prepared in the same manner as in Example 1, except that the conditions for forming the silicon oxide layer were changed to the conditions shown in Table 2 below.
  • the total thickness of the silicon oxide layer by PE-CVD was 8.0 ⁇ m.
  • the maximum temperature of the substrate surface on the side where the silicon oxide layer was laminated by the PE-CVD method was about 115 ° C.
  • the thickness of each layer is shown in Table 3 below.
  • Example 1 A polymer substrate with a hard coat layer was prepared in the same manner as in Example 1, except that the base cured layer coating agent (P2) was used instead of the base cured layer coating agent (P1).
  • Example 1 the conditions for forming the silicon oxide layer were (pretreatment step) Ar (argon) introduction amount: 50 sccm, specified pressure: 20 Pa, plasma output: 6%, time: 60 seconds, (film formation step) TMS (Trimethylsilane) Polymer with hard coat layer in the same manner as in Example 1, except that the introduced amount was 20 sccm, the introduced amount of oxygen was 100 sccm, the specified pressure was 25 Pa, the plasma output was 6%, and the time was 2000 seconds. A substrate was created.
  • Ar argon
  • introduction amount 50 sccm
  • specified pressure 20 Pa
  • plasma output 6%
  • time 60 seconds
  • TMS Trimethylsilane
  • Example 3 A polymer substrate with a hard coat layer was prepared in the same manner as in Example 1, except that the conditions for forming the silicon oxide layer were changed to the conditions shown in Table 7 below.
  • the thickness of the entire silicon oxide layer by PE-CVD was 6.0 ⁇ m when calculated by rounding off the second decimal place.
  • the maximum temperature of the substrate surface on the side where the silicon oxide layer was stacked by the PE-CVD method was about 110 ° C.
  • the thickness of each layer is shown in Table 8 below.
  • Example 4 A polymer substrate with a hard coat layer was produced in the same manner as in Example 1, except that the conditions for forming the silicon oxide layer were changed to the conditions shown in Table 7 below.
  • the thickness of the entire silicon oxide layer by PE-CVD was 6.1 ⁇ m, calculated by rounding off the second decimal place.
  • the maximum temperature of the substrate surface on the side where the silicon oxide layer was stacked by the PE-CVD method was about 110 ° C.
  • the thickness of each layer is shown in Table 8 below.
  • Example 5 A polymer substrate with a hard coat layer was prepared in the same manner as in Example 1, except that the conditions for forming the silicon oxide layer were changed to the conditions shown in Table 7 below.
  • the thickness of the entire silicon oxide layer obtained by the PE-CVD method was 4.3 ⁇ m when calculated by rounding off the second decimal place.
  • the maximum temperature of the substrate surface on the side where the silicon oxide layer was laminated by the PE-CVD method was about 105 ° C.
  • the thickness of each layer is shown in Table 8 below.
  • Example 6 A polymer substrate with a hard coat layer was prepared in the same manner as in Example 1, except that the conditions for forming the silicon oxide layer were changed to the conditions shown in Table 7 below.
  • the thickness of the entire silicon oxide layer by PE-CVD was 5.9 ⁇ m, calculated by rounding off the second decimal place.
  • the maximum temperature of the substrate surface on the side where the silicon oxide layer was stacked by the PE-CVD method was about 110 ° C.
  • the thickness of each layer is shown in Table 8 below.
  • the active energy ray-curable primer composition was applied to a polycarbonate resin plate by air spraying so that the dry film thickness was 8 ⁇ m. Subsequently, the polycarbonate resin plate was preheated at 80 ° C. for 10 minutes, and then irradiated with active energy rays at a dose of 2,000 mJ / cm 2 using a high-pressure mercury lamp, thereby forming a cured coating layer. Produced.
  • an inorganic material layer was laminated thereon using a plasma CVD apparatus so as to have a thickness of 5 ⁇ m, thereby obtaining a polymer substrate with a hard coat layer.
  • a UV curable resin (trade name "UVHC7800” Momentive Performance Material) is used as a first hard coat layer on the surface of a base film, a 188 ⁇ m thick PMMA film (trade name "RT050” manufactured by Kuraray Co., Ltd.).
  • RT050 trade name "RT050” manufactured by Kuraray Co., Ltd.
  • An organic-inorganic hybrid resin (product name “NH-1000G” manufactured by Nippon Soda Co., Ltd.) was laminated on the surface thereof as an anchor coat layer by a bar code method. At this time, a filler (trade name “NH-9100S” manufactured by Nippon Soda Co., Ltd.) was mixed with the raw material resin.
  • a plasma-deposited layer made of HMDSO Hexamethyldisilozane (manufactured by Shin-Etsu Chemical Co., Ltd.) was laminated to obtain a polymer substrate with a hard coat layer.
  • HMDSO Hexamethyldisilozane
  • the thickness of the anchor coat layer was set to 7.0 ⁇ m
  • the amount of the filler added was set to 2.5%
  • the thickness of the second hard coat layer was set to 150 nm.
  • the composite coating composition is flow coated on a surface-cleaned Lexan polycarbonate plate (150 mm ⁇ 150 mm ⁇ 4 mm thick) as a cured coating film to a thickness of about 9 to 14 ⁇ m, and heated at 120 ° C. for 60 minutes. After curing, an intermediate layer was obtained.
  • a film composed of silicon, oxygen, carbon and hydrogen atoms was laminated as the outermost layer on the film by plasma polymerization to obtain a laminate.
  • the substrate on which the cured coating of the composite coating composition was formed was cleaned by hand with a lint-free cloth using isopropyl alcohol and deionized water.
  • plasma polymerization was performed in a vacuum chamber by a continuous double-sided expansion thermal plasma process.
  • the two plasma coating locations consist of an expanded thermal plasma source train that creates an argon plasma jet at supersonic speed. The plasma jet expanded at the plasma coating location and reacted with the organosilicon reagent and oxidant injected directly into the chamber.
  • the organosilicon reagent was octamethylcyclotetrasiloxane (manufactured by Gelest) and the oxidizing agent was industrial grade oxygen 99% (manufactured by Airgas).
  • the substrate was continuously transferred through the chamber and heated to about 40-70 ° C. before entering the coating location.
  • Respect Comparative Examples 1-9 the details of the chemical composition Si x C y H z of the silicon oxide layer (CVD layer) shown in Table 9 below, nano-indentation measurements, surface roughness, and the infrared absorption peak intensity ratio of Detail Is shown in Table 10 below, and the results of the performance evaluation of the polymer substrate with a hard coat layer are shown in Table 11 below.
  • Abrasion resistance "in Table 12 was evaluated based on the results of nanoindentation measurement of the silicon oxide layer shown in Tables 5 and 10, and the results of Taber abrasion shown in Tables 6 and 11.
  • the evaluation of “wear resistance” is “VG” when the indentation hardness is 4.5 GPa or more and the Taber abrasion ⁇ H is 1.0% or less; “VG”; is the indentation hardness 4.5 GPa or more? Or “G” when the Taber abrasion ⁇ H is 1.0% or less; “P” when the indentation hardness is 4.5 GPa or less and the Taber abrasion ⁇ H is 1.0% or more.
  • Examples 1 and 2 differ only in the conditions for forming the silicon oxide layer by the PE-CVD method. However, weather resistance, Taber abrasion, high hardness, boiling water performance, water resistance, heat resistance Good results were obtained in both performance.
  • the base cured layers of Examples 1 and 2 contain 10 to 90 parts by weight of a polyfunctional acrylate, 90 to 10 parts by weight of a silicon compound hydrolyzed condensate containing the composite resin (A), and have a thickness of 1 to 10 parts.
  • the silicon oxide layer satisfies the following (a 1 ) requirements at least at a position of 0.04 ⁇ m in the thickness direction from the interface of the silicon oxide layer in contact with the base hardened layer, and has the following (a 3 ) By meeting the requirements: (A 1 ) When the chemical composition is represented by SiO x C y H z , x is in the range of 1.93 to 1.98, y is in the range of 0.04 to 0.15, and z is Being in the range of 0.10 to 0.50, (A 3 ) When the chemical composition is represented by SiO x C y H z , x is in the range of 1.94 to 2.02, y is in the range of 0.05 to 0.16, and z is Must be in the range of 0.20 to 0.50.
  • the cured underlayers of Examples 1 and 2 are described below in (a 1 ) to (c 1 ) at a position of 0.04 ⁇ m in the thickness direction from the interface between the cured underlayer and the silicon oxide layer. It meets all of the requirements and, on the surface opposite the interface, satisfies all of the preferred requirements described in (b 3 ) to (c 3 ) below:
  • (B 1) IR absorbance ratio of the wave number 930 cm -1 and 1020cm -1 ( ⁇ 930 / ⁇ 1020 ) may be in the range of 0.10-0.20,
  • (C 1) IR absorbance ratio of the wave number 1280 cm -1 and 1020cm -1 ( ⁇ 1280 / ⁇ 1020 ) may be in the
  • Example 3 is different from Example 1 only in the conditions for forming the silicon oxide layer by the PE-CVD method. 2), good results were obtained in all of Taber abrasion, high hardness, boiling water performance, water resistance, and heat resistance, and good results were also obtained in accelerated weather resistance.
  • the input power is directly increased to increase the ratio of the input power to that in the first embodiment. Since a dense high-hardness layer is formed, better results are obtained in the high hardness than in the first embodiment. Have been.
  • Example 4 differs from Example 1 only in the conditions for forming the silicon oxide layer by the PE-CVD method, but is described in the above “(1) Examples 1 and 2”. Among the requirements, the preferred requirements described in (a 1 ) to (c 1 ) are not satisfied. As a result, in Example 4, although extremely high abrasion resistance was obtained, the result of Example 1 was better with respect to boiling water resistance and heat resistance.
  • Example 1 and Comparative Example 1 are the same under the plasma treatment conditions for the underlying cured layer and the conditions for forming the silicon oxide layer by the PE-CVD method (Tables 2 and 7). Please refer to).
  • Comparative Example 1 although good results were obtained in abrasion resistance, high hardness, heat resistance, and the like, excellent weather resistance was not obtained.
  • the composite resin (A) was not contained in the silicon compound hydrolyzed condensate of the base hardening layer coating agent, and did not satisfy the requirements defined in Claim 1. As a result, it was not possible to obtain a polymer substrate provided with a hard coat which has excellent weather resistance, abrasion resistance, high hardness, and heat resistance.
  • Example 1 and Comparative Example 2 differ only in the conditions for forming the silicon oxide layer by the PE-CVD method.
  • Comparative Example 2 in the (a) chemical composition SiO x C y H z on the surface of the silicon oxide layer, x is out of the range of the requirement described in “(1) Examples 1 and 2”, and The ratio of (b 3 ) infrared absorbance ( ⁇ 930 / ⁇ 1020 ) on the surface was also out of the preferred range, and the abrasion resistance was insufficient. Further, good results were not obtained with respect to heat resistance and boiling water performance.
  • Example 1 and Comparative Examples 3 and 5 differ only in the conditions for forming the silicon oxide layer by the PE-CVD method.
  • Comparative Examples 3 and 5 in the (a 3 ) chemical composition SiO x C y H z of the surface of the silicon oxide layer, x was out of the range described in “(1) Examples 1 to 4” above.
  • the ratio of (b 3 ) infrared absorbance ( ⁇ 930 / ⁇ 1020 ) of the surface was out of the preferred range, so that the abrasion resistance was insufficient.
  • Example 1 and Comparative Example 4 differ only in the conditions for forming the silicon oxide layer by the PE-CVD method.
  • Comparative Example 4 in the (a 3 ) chemical composition SiO x C y H z of the surface of the silicon oxide layer, x, y, and z were within the range of the requirements described in “(1) Examples 1 to 4” above. Since the ratio of (b 3 ) infrared absorbance ( ⁇ 930 / ⁇ 1020 ) of the surface was out of the preferable range, the high hardness was insufficient.
  • Example 1 and Comparative Example 6 differ only in the conditions for forming the silicon oxide layer by the PE-CVD method.
  • Comparative Example 6 has a high hardness layer.
  • the formation of the silicon oxide layer was completed in the bulk layer, and in the (a 3 ) chemical composition SiO x C y H z on the surface of the silicon oxide layer, x, y, and z were the same as those in “(1) Example. (1) to ( 4 ), and (b 3 ) the ratio of infrared absorbance ( ⁇ 930 / ⁇ 1020 ) is out of the preferred range, so that Taber abrasion, high hardness, boiling water resistance, Heat resistance was insufficient.
  • Example 1 and Comparative Examples 7 and 8 were different from each other in the type of the underlying cured layer and the conditions for forming the silicon oxide layer by the PE-CVD method.
  • x, y, and z are as described in “(1) Examples 1 to 4) is out of the range of the requirements described in “4.
  • the ratio of (b 1 ) infrared absorbance of the silicon oxide layer ( ⁇ 930 / ⁇ 1020 ) and the ratio of (c 1 ) infrared absorbance ( ⁇ 1280 / ⁇ 1020) ) Is out of the preferred range.
  • Example 1 and Comparative Example 9 are different from each other in the type of the underlying cured layer and the conditions for forming the silicon oxide layer by the PE-CVD method.
  • x, y and z are as described in “(1) Examples 1 to 4” above. It is out of the required range, and the ratio of (b 1 ) infrared absorbance ( ⁇ 930 / ⁇ 1020 ) and the ratio of (c 1 ) infrared absorbance ( ⁇ 1280 / ⁇ 1020 ) are out of the preferred ranges.
  • the polymer substrate with a hard coat layer of the present invention has excellent surface abrasion resistance comparable to that of inorganic glass, and also has high environmental resistance that can be used for a long period of time even under severe use environments, for example, It can be used for automotive window materials, building materials, surface protection plates for solar cells, etc., and is extremely useful.

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Abstract

La présente invention permet d'obtenir un substrat polymère doté d'une couche de revêtement dur qui présente à la fois une résistance élevée à l'environnement et une résistance élevée à l'abrasion. Ce substrat polymère doté d'une couche de revêtement dur comprend un substrat polymère (50), une couche de base durcie (70) et une couche d'oxyde de silicium (80), qui ont été stratifiées directement dans cet ordre, la couche de base durcie (70) étant de 1 à 20 µm d'épaisseur et contenant un condensat hydrolytique d'un composé de silicium, le condensat hydrolytique d'un composé de silicium contenant une résine composite (A) à partir de la liaison, par l'intermédiaire d'une liaison spécifique, d'un segment de polymère à base de vinyle (a2) et d'un segment polysiloxane (a1) présentant une unité structurale spécifique et un groupe silanol et/ou un groupe silyle hydrolysable, la couche d'oxyde de silicium (80) satisfaisant des conditions (a1) au niveau d'une position qui est de 0,04 µm dans la direction de l'épaisseur à partir de l'interface entre la couche de base durcie (70) et la couche d'oxyde de silicium (80), et satisfaisant des conditions (a3) sur la surface opposée à l'interface : (a1) lorsque la composition chimique est représentée par SiOxCyHz, x est dans une plage de 1,93 à 1,98, y est dans une plage de 0,04 à 0,15 et z est dans une plage de 0,10 à 0,50 ; et (a3) lorsque la composition chimique est représentée par SiOxCyHz, x est dans une plage de 1,94 à 2,02, y est dans une plage de 0,05 à 0,16 et z est dans une plage de 0,20 à 0,50.
PCT/JP2019/038783 2018-10-02 2019-10-01 Substrat polymère doté d'une couche de revêtement dur WO2020071379A1 (fr)

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JPWO2021172356A1 (fr) * 2020-02-26 2021-09-02

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WO2016068236A1 (fr) * 2014-10-30 2016-05-06 Dic株式会社 Stratifié
JP2016216589A (ja) * 2015-05-19 2016-12-22 Dic株式会社 ポリシロキサン、樹脂組成物、塗料及び積層体

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JP2006328354A (ja) * 2005-03-08 2006-12-07 Dainippon Ink & Chem Inc 紫外線硬化性樹脂組成物、紫外線硬化性塗料及び塗装物。
JP2014531334A (ja) * 2011-08-26 2014-11-27 エグザテック・リミテッド・ライアビリティー・カンパニーＥｘａｔｅｃ，ＬＬＣ． 有機樹脂積層体、その製造及び使用方法、並びに有機樹脂積層体を含む物品
JP2015093400A (ja) * 2013-11-11 2015-05-18 Dic株式会社 積層体
WO2015147295A1 (fr) * 2014-03-27 2015-10-01 帝人株式会社 Substrat polymère comprenant une couche de revêtement dur et procédé de fabrication d'un tel substrat polymère
WO2016068236A1 (fr) * 2014-10-30 2016-05-06 Dic株式会社 Stratifié
JP2016216589A (ja) * 2015-05-19 2016-12-22 Dic株式会社 ポリシロキサン、樹脂組成物、塗料及び積層体

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JPWO2021172356A1 (fr) * 2020-02-26 2021-09-02
WO2021172356A1 (fr) * 2020-02-26 2021-09-02 富士フイルム株式会社 Stratifié à revêtement dur
JP7440607B2 (ja) 2020-02-26 2024-02-28 富士フイルム株式会社 ハードコート積層体

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