JP4176538B2 - Polymer resin laminate and window material - Google Patents

Description

【０１１５】
実施例および比較例における架橋樹脂層と蒸着膜の膜厚、物性の評価結果と、高分子樹脂積層体の評価評価の結果を示す表である。
【０１１６】
【発明の効果】
ポリカーボネート等の硬度や耐摩耗性の低い樹脂成形物に対して、本願発明を適用することにより、極めて優れた耐摩耗性を有する高分子樹脂積層体を得ることができ、各種車両や建築物の窓材、その他の幅広い用途に利用することができるようになった。
【図面の簡単な説明】
【図１】実施例２における基板の真空蒸着装置内での配置を示す模式図である。
【図２】比較例３における基板の真空蒸着装置内での配置を示す模式図である。
【図３】ナノインデンテーション測定の負荷／除荷曲線についての説明図である。
【符号の説明】
１． 基板
２． 蒸着源
３． 電子ビーム
４． 基板
５． 蒸着源
６． 電子ビーム
７． 負荷曲線
８． 除荷曲線
９． 除荷曲線終点の変位
１０．最大変位[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer resin laminate having an extremely high wear resistance, and window materials for various vehicles and buildings using the polymer resin laminate (here, the window material is at least transparent). Indicates what is possible).
[0002]
[Prior art]
Polymer resin materials are used in a variety of applications, taking advantage of characteristics such as impact resistance, light weight, and workability. In particular, in recent years, there has been a movement to apply a polymer resin molded article having improved surface hardness and wear resistance to the use of window materials for various vehicles utilizing its light weight and safety. In such applications, high abrasion resistance comparable to glass and weather resistance outdoors are required. For example, in automobiles, a high level of wear resistance is required to prevent scratches when the wiper is activated and scratches when the window is raised and lowered, and it is not assumed to be used in extremely high temperature and humidity environments. Must not.
[0003]
As a method for improving the surface hardness and wear resistance of a polymer resin molded product, for example, there is a method of coating an acrylic resin layer on the surface of the polymer resin molded product and further coating a siloxane-based cured film thereon. For example, a coating composition is described in which colloidal silica is added to a condensate of alkyltrialkoxysilane and tetraalkoxysilane (see, for example, Patent Documents 1 to 3).
[0004]
In all of these examples, layers are deposited by wet coating, but recently, a method of laminating layers of inorganic oxides by a vacuum process such as vacuum deposition or CVD (chemical vapor deposition) has been proposed. . For example, there has been proposed an electron beam evaporation method in which a material such as silicon oxide is evaporated by heating with an electron beam in a vacuum chamber, and evaporated particles are deposited on a substrate placed in the vacuum chamber to stack layers ( For example, see Patent Document 4).
[0005]
A method of evaporating aluminum oxide or silicon oxide by electron beam heating, passing plasma generated in the space between the deposition source and the substrate, increasing the kinetic energy of the deposited particles, and then depositing on the substrate (HAD process) has been proposed (see, for example, Non-Patent Documents 1 and 2).
[0006]
[Patent Document 1]
Japanese Unexamined Patent Publication No. Sho 63-27879
[Patent Document 2]
JP-A-1-306476
[Patent Document 3]
JP 2000-318106 A
[Patent Document 4]
JP 2002-127286 A
[Non-Patent Document 1]
M.M. Krug, “Abrasion resisting coatings on plastic by PVD high rate deposition”, Proceedings of the 3rd-ICCG2000, p577
[Non-Patent Document 2]
Takuichi Suzuki et al., “Surface Treatment Technology Forefront Report (4) Fraunhofer Electron Beam Plasma Laboratory (III)”, Industrial Materials, Vol. 49No. 7 p72 (July 2001 issue)
[0007]
[Problems to be solved by the invention]
However, the polymer resin laminate formed by the above-described wet coating has a poor hardness in comparison with the glass plate to be substituted because the cured siloxane film has low hardness.
[0008]
On the other hand, a polymer resin laminate in which an inorganic oxide film is formed by a vacuum process can provide a relatively high film hardness and excellent wear resistance. In fact, in the previous studies by the present inventors, wear is caused by laminating an electron beam deposited film of silicon dioxide in a predetermined Young's modulus and film thickness range on a polycarbonate substrate via an ultraviolet curable resin layer. It has been confirmed that the same value as the glass plate used as the control sample can be obtained as an increase (ΔH) in the haze value when the Taber abrasion test of 1000 revolutions using CS-10F is performed. .
[0009]
However, for example, when the CS-10 wear wheel is used instead of the CS-10F wear wheel as a condition of the Taber wear test, the haze value is increased more than the test result of the glass plate. In many cases, (ΔH) was slightly increased, and the results were somewhat inferior in wear resistance.
[0010]
From these things, the present inventors made it a subject to implement | achieve the polymer resin laminated body which can obtain the abrasion resistance completely equivalent to a glass plate also under these severer abrasion test conditions, and came to this invention. .
[0011]
[Means for Solving the Problems]
That is, the present invention is as follows.
1. A polymer resin laminate in which a crosslinked resin layer having a thickness of 3 to 100 μm and a silicon oxide layer having a thickness of 4 to 25 μm are laminated in this order on at least one surface of the polymer resin substrate, The layer is a cross-linked resin layer having a Young's modulus in the range of 5 to 15 GPa when nanoindentation measurement is performed under a maximum load of 1 mN, and the silicon oxide layer has a Young's modulus in the range of 45 to 125 GPa. A polymer resin laminate, which is a silicon oxide layer having a displacement value at the end point of the load / displacement curve within a range of 0 to 40% of the maximum displacement value.
2. 1 polymer resin using an actinic ray curable resin layer containing a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in a molecule or in a unit repeating structure as a main component of a precursor material as a cross-linked resin layer Laminated body.
3. 1. A polymer resin laminate according to claim 1, wherein a thermosetting resin layer containing a hydrolyzate of organosilicon trialkoxide as a main component of a precursor material is used as a crosslinked resin layer.
4). As the silicon oxide layer, a silicon oxide layer formed by any one of an electron beam evaporation method, an ion plating method, a sputtering method, a chemical vapor deposition method (CVD method), or a combination of these methods is used. 3. The polymer resin laminate according to any one of 3 above.
5. The polymer resin laminate according to any one of 1 to 4, wherein the thickness of the polymer resin substrate is in the range of 1 to 20 mm.
6). The polymer resin laminate according to any one of 1 to 5, wherein the polymer resin substrate is a molded substrate made of a polycarbonate resin.
7). The window material for vehicles or buildings which contains the polymer resin laminated body in any one of said 1-6 as a component at least.
[0012]
In the following, the present invention will be described in more detail.
In order to achieve the same level of wear resistance as that of a glass plate under more severe wear conditions, which is the subject of the present invention, the thickness and nanoindent physical properties of the silicon oxide layer and the crosslinked resin layer are set within a predetermined range as described later. It turns out that things are good.
[0013]
First of all, the thickness of the silicon oxide layer was preferably 4 to 25 μm, more preferably 5 to 20 μm. When the thickness is less than 4 μm, the wear resistance tends to be insufficient, and when it exceeds 25 μm, a decrease in the adhesion of the silicon oxide layer is often observed.
[0014]
The nanoindentation physical property of the silicon oxide layer is preferably set to a Young's modulus in the range of 45 to 125 GPa, more preferably in the range of 50 to 125 GPa, and still more preferably in the range of 55 to 125 GPa under the measurement conditions described in the examples. Is preferred. When the Young's modulus is less than 45 GPa, the wear resistance is often insufficient. Here, the value of 125 GPa, which is the upper limit, is described as the maximum value obtained with the silicon oxide film.
[0015]
Furthermore, it is preferable that the displacement value at the end point of the load / displacement curve under the measurement conditions described in the examples (the displacement value immediately after the load becomes zero at the end of the unloading process) is as small as possible, and at least the displacement value described above. Is in the range of 0 to 40% of the maximum displacement value, more preferably 0 to 30%, still more preferably 0 to 20%, and most preferably 0 to 10%. When this ratio exceeds 40%, the wear resistance is often insufficient. The ratio between the displacement at the end point and the maximum displacement is considered to indicate the degree of plastic deformation of the silicon oxide layer. From these results, the plastic deformation of the silicon oxide layer is necessary to achieve higher wear resistance. It is considered preferable to make the property smaller.
[0016]
Such a silicon oxide layer having a high Young's modulus and plastic deformability is formed by using a vacuum process such as an electron beam evaporation method, an ion plating method, a sputtering method, or a CVD method (chemical vapor deposition method). It is preferable.
[0017]
Furthermore, for example, a combination of different processes such as a combination of an electron beam evaporation method and a sputtering method (laminated film) or a combination of an ion plating method and a CVD method (mixed film) can be suitably used. .
[0018]
The silicon oxide layer can be used even if it is not silicon dioxide having a perfect chemical composition but silicon oxide having an oxidation number of less than 2 or a material that contains some elements other than oxygen and silicon. Examples of such dissimilar materials include dissimilar elements such as titanium, alumina, zirconium, lead, cerium, zinc, and tin, various organosilicon compounds, organometallic compounds, and polymer resins such as acrylic resins and polyethylene resins. Can be mentioned.
[0019]
The thickness of the cross-linked resin layer was preferably 3 to 100 μm, more preferably 5 to 100 μm, and still more preferably 10 to 100 μm. When the thickness is less than 3 μm, the wear resistance tends to be insufficient. On the other hand, when it exceeds 100 μm, it is difficult to form a crosslinked resin layer, and the adhesion to the polymer resin substrate is often reduced.
[0020]
The Young's modulus of the crosslinked resin layer measured by nanoindentation is preferably in the range of 5 to 15 GPa, more preferably in the range of 6 to 15 GPa, under the measurement conditions described in the examples. When the Young's modulus is less than 5 GPa, a decrease in wear resistance is often observed, and when it exceeds 15 GPa, the adhesion between the crosslinked resin layer and the polymer resin substrate or silicon oxide layer is often decreased.
[0021]
Further, the cross-linked resin layer preferably has a water absorption rate of approximately 0 to 2%, more preferably 0 to 1.5%, and still more preferably 0 to 1%. If the water absorption rate exceeds 2%, the vacuum process for forming the silicon oxide layer is often adversely affected.
[0022]
Further, the cross-linked resin layer preferably has a glass transition temperature or softening temperature of 120 ° C. or higher, more preferably 150 ° C. or higher. These can be measured by, for example, endothermic peaks in differential thermal analysis (DSC) (the temperature of the main peak derived from the main component when multiple peaks appear), thermal scanning dynamic viscoelasticity analysis, or the like. .
[0023]
As the crosslinked resin layer having such physical properties, for example, an actinic ray curable resin mainly containing a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in a molecule or a unit repeating structure. Preferred examples include a layer, and a thermosetting resin layer mainly containing a hydrolyzate of an organosilicon trialkoxide such as methyltrimethoxysilane or methyltriethoxysilane.
[0024]
As monomers and oligomers that are precursor materials for the actinic ray curable resin layer, it is less preferable to contain a hydrophilic group such as a hydroxyl group or an amino group in the side chain or terminal in the molecule or unit repeating structure from the viewpoint of water absorption. It is preferable that a hydrophobic group such as an aliphatic chain or an alicyclic ring is contained in an appropriate ratio, and a cyclic structure such as a cyclo ring, an isocyanuric ring, a cyanuric ring, isophorone, or 1,3-dioxane is included from the viewpoint of heat resistance. Things are preferable.
[0025]
More specifically, for example, a polyfunctional (meth) acrylate containing a cyclo ring (eg, dicyclopentanyl diacrylate, dicyclopentanyl dimethacrylate), an isocyanuric ring, a polyfunctional acrylate containing a cyanuric ring (eg, isocyanuric acid) Ethylene oxide-modified triacrylate, cyanuric acid ethylene oxide-modified triacrylate), polyfunctional urethane acrylate obtained by modifying bifunctional isocyanate (for example, hexamethylene diisocyanate, isophorone diisocyanate, hexaacrylate obtained by modifying tolylene diisocyanate), 1, Polyfunctional acrylate containing 3-dioxane, polyester acrylate obtained by modifying phthalic acid, trimethylolpropane tri (meth) acrylate and / or ethylene Preferred examples include xylene and / or propylene oxide modified products, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and the like. And polyfunctional (meth) acrylates having various structures.
[0026]
These precursor monomers and oligomers are diluted with an appropriate solvent as needed, and then wet-coated on a polymer resin substrate, and then an appropriate amount of actinic rays such as ultraviolet rays (which may include visible rays) and electron beams are applied. The actinic ray cured layer is cured and formed by irradiation.
[0027]
In these actinic ray-cured layers, addition of an appropriate amount of subcomponents may be preferable, and organic silicon compounds such as γ- (meth) acryloxypropyltrimethoxysilane and polyether-modified polydimethylsiloxane, and the average particle size may be Addition of fine particles such as silicon oxide and acrylic resin of about 3 to 30 nm, photopolymerization initiator, photopolymerization initiation assistant, ultraviolet absorber, light stabilizer, heat stabilizer and the like is performed as necessary.
[0028]
In addition, as a coating method to the polymeric resin substrate of the precursor material of these crosslinked resin layers, for example, dip coating method, spray coating method, spin coating method, (doctor) knife coating method, direct gravure coating method, offset gravure method , Reverse gravure method, reverse roll coating method, (Meyer) bar coating method and the like can be applied.
[0029]
For the purpose of adjusting the viscosity of the coating solution suitable for coating, the precursor material is diluted with various solvents as necessary. Solvents include ethyl alcohol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, tertiary butyl alcohol, 1 methoxy 2 propanol, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, diacetone alcohol, etc. Illustrated.
[0030]
In addition, the polymer resin substrate coated with the precursor material of the crosslinked resin layer can be used for drying and removing residual solvent in the precursor material, improving the leveling property, improving the adhesion between the actinic ray cured layer and the polymer resin substrate, etc. For various purposes, it is often preferable to raise the temperature to 50 to 130 ° C. once before irradiation with actinic rays.
[0031]
In addition, when laminating the cross-linked resin layer on the polymer resin substrate, if necessary, a primer layer having an effect of improving the adhesion between the polymer resin substrate and the cross-linked resin layer is laminated, or on the polymer resin substrate. Various surface treatments may be performed.
[0032]
As such a primer layer, a layer mainly composed of an acrylic thermoplastic resin is preferably exemplified, and as the surface treatment, various plasma treatments, corona treatment, UV-ozone treatment, high-pressure hot water or Suitable methods include surface cleaning with water vapor and solvent cleaning with alcohol.
[0033]
The average thickness of the polymer resin substrate is preferably in the range of about 1 to 20 mm, more preferably in the range of 2 to 20 mm, and still more preferably in the range of 3 to 15 mm. If the thickness is less than 1 mm, the mechanical strength as a window material tends to be insufficient, and if it exceeds 20 mm, the influence of an increase in the weight of the substrate becomes large.
[0034]
Examples of the polymer resin substrate include acrylic resins such as polycarbonate, polyarylate, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, and various polyolefin resins (for example, trade name “Arton” of JSR Corporation, trade name of Nippon Zeon Corporation). And a polymer resin substrate formed by molding “ZEONOR”) or the like.
[0035]
Among these, in particular, a polymer resin substrate formed by molding a polycarbonate resin from the viewpoint of impact resistance, transparency, moldability, lightness, etc. is most preferably used in window materials for various vehicles and buildings. Is particularly preferably used.
[0036]
Here, the polycarbonate means a polycondensate of an aromatic dihydroxy compound and a carbonic acid bond-forming compound.
[0037]
Specific examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2 -Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 4,4-dihydroxyphenyl-1,1′-m-diisopropylbenzene, 4,4′-dihydroxyphenyl-9 Bis (4-hydroxyaryl) alkanes such as 1,9-fluorene, 1,1-bis (4-hydroxypheny ) Cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-methyl-1- (4-hydroxyphenyl) -4- (dimethyl-4-hydroxyphenyl) methyl-cyclohexane, 4- [1- [ 3- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] -phenol, 4,4 ′-[1-methyl-4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol Bis (hydroxy) such as 2,2,2 ′, 2′-tetrahydro-3,3,3 ′, 3′-tetramethyl-1,1′-spirobis- [1H-indene] -6,6′-diol Aryl) cycloalkanes, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 4,4′-dihydroxy Dihydroxy aryl ethers such as 3,3′-dimethylphenyl ether, 4,4′-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4 Dihydroxydiaryl sulfoxides such as' -dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl Dihydroxy diaryl sulfones such as diphenyl sulfone, dihydroxy diaryl isatins such as 4,4′-dihydroxydiphenyl-3,3′-isatin, dihydroxy diaryls such as 3,6-dihydroxy-9,9-dimethylxanthene Lillexanthenes, resorcin, 3-methyl resorcin, 3-ethyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin, hydroquinone, 2-methylhydroquinone, 2-ethylhydroquinone Dihydroxybenzenes such as 2-butylhydroquinone, 2-t-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, 4,4′-dihydroxydiphenyl, 3,3′-dichloro-4,4′-dihydroxy And dihydroxydiphenyls such as diphenyl. Of these, 2,2-bis (4-hydroxyphenyl) propane is preferred.
[0038]
Specific examples of the carbonic acid bond-forming compound include phosgene such as phosgene, trichloromethyl chloroformate, and bis (trichloromethyl) carbonate, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, and diethyl carbonate. Examples thereof include alkylaryl carbonates such as dialkyl carbonates, methylphenyl carbonate, and ethylphenyl carbonate.
[0039]
When phosgene is used, the polycarbonate is produced by a solution method, and when carbonates having a carbonate bond are used, the polycarbonate is produced by a melting method. Among the carbonate esters, diphenyl carbonate is preferably used.
[0040]
These compounds can be used alone or in combination.
[0041]
In addition, what contains another component as a copolymerization or a blend component is also contained in the category of a polycarbonate.
[0042]
The most suitable for the present invention is polycarbonate using 2,2-bis (4-hydroxyphenyl) propane as the aromatic dihydroxy compound and phosgene or carbonate ester having carbonate bond as the carbonate bond forming compound. It is.
[0043]
When the copolymerization rate or blending rate of the other components is high, the characteristics of the polycarbonate are reduced. Therefore, the copolymerization rate or blending rate is preferably 20% by weight or less, and more preferably 10% by weight or less.
[0044]
In addition, a substrate obtained by laminating a film made of a resin other than polycarbonate, which contains an ultraviolet absorber and has excellent weather resistance of the resin itself, is preferably used on at least one surface of such a polycarbonate molded substrate. By using such a substrate and using it so that the substrate surface on which the film is laminated becomes the surface on the outdoor side (the surface on which sunlight is mainly incident), the hardness and weather resistance of the polymer resin laminate are improved. I can do things.
[0045]
The film preferably has a thickness of about 10 to 200 μm from the viewpoint of handleability and suitability for laminating, and may be laminated to a pre-formed polycarbonate substrate, or may be subjected to adhesive processing, or may be integrally formed by a coextrusion method. Alternatively, it may be integrated with the polycarbonate by insert molding in an injection mold or two-color molding.
[0046]
According to such a method, the color and physical property deterioration of the laminated film itself due to ultraviolet irradiation are extremely small, and a polycarbonate mixed with an ultraviolet absorber in an amount capable of absorbing almost 100% of ultraviolet rays over a long period of time is used. Since no ultraviolet rays are incident on the substrate, there is no worry of coloring or deterioration of physical properties due to ultraviolet rays. As such a resin film, a film made of an acrylic resin is particularly preferable, and as a resin substrate laminated and integrated on a polycarbonate, for example, Teijin Kasei's trade name “Panlite PC-8111” is preferably exemplified. The
[0047]
The polymer resin laminate of the present invention preferably has high transparency of the laminate from the necessity for its use. Specifically, the haze (cloudiness value) of the laminate is preferably 5% or less, more preferably 3% or less, still more preferably 2% or less, and most preferably 1% or less.
[0048]
The light transmittance of the polymer resin laminate is generally desired to be high, and is preferably 50% or more, more preferably 70% or more, and still more preferably 85% in terms of the total light transmittance. Above, most preferably 90% or more. However, depending on the use of the polymer resin laminate, a high light transmittance may not always be desired.For example, in a window material for a rear seat of an automobile, for the purpose of suppressing an increase in the temperature inside the vehicle due to direct sunlight, When the light transmittance of the laminate is intentionally reduced by a method such as mixing a visible light absorber (pigment, dye, etc.) in the polymer resin substrate, the above preferred range of the total light transmittance You may deviate from.
[0049]
【Example】
The preferred embodiments of the present invention will be described below. However, the present invention is not limited to these examples. In addition, the characteristic evaluation in an Example and a comparative example was performed in the following ways.
[0050]
1. Measurement of thickness of crosslinked resin layer and silicon oxide layer
It calculated | required based on the cross-sectional observation image by a scanning electron microscope (SEM).
[0051]
2. Measurement of Young's modulus and plastic deformation by nanoindentation
Nanoindentation measurement of a vapor deposition layer of silicon oxide and an actinic ray hardening layer was performed using ENT-1100a manufactured by Elionix Co., Ltd. The measurement position was the center of the sample (near the intersection of diagonal lines).
[0052]
That is, using a triangular pyramid indenter with a ridge interval of 115 degrees, the maximum load value is equally divided into 250 to increase the pushing load in steps (4 μN / step for a maximum load of 1 mN) in 10 seconds. After reaching the maximum load and holding the maximum load for 1 second, the pushing load is gradually reduced and the load value is returned to 0 in 10 seconds.
[0053]
The measurement is performed at a constant temperature of 25 ° C., and after the temperature of the measuring device and the sample is sufficiently stabilized, the load / displacement curve is measured under the condition of a maximum load of 1 mN, and Young's modulus and plastic deformability are measured. went. In addition, the measurement was performed 5 times continuously, and the average value was used as the measurement value.
[0054]
Regarding plastic deformability, the displacement value at the final step of the unloading process, that is, the displacement value immediately after the load returns to 0, the maximum displacement (the displacement value immediately after holding for 1 second at the maximum load). Expressed as a percentage (%).
[0055]
In measurement, there may be an error in measurement data due to wear of the tip of the indenter, etc. Before measuring each sample, first measure a commercially available silicon wafer under the condition of a maximum load of 1 mN. The sample was measured after confirming that the maximum displacement value when the silicon wafer was pushed in was in the range of 55 nm ± 3 nm. When the maximum displacement value deviated from this range, a new indenter was replaced.
[0056]
For reference, Table 1 also shows the results of measuring commercially available plate glass having a thickness of 5 mm and a molded sheet of polycarbonate having a thickness of 0.4 mm (Teijin Kasei “Panlite PC-1151”) under the measurement conditions.
[0057]
3. Measurement of haze value and total light transmittance
Measurement was performed using a measuring instrument (trade name “COH-300A”) manufactured by Nippon Denshoku Industries Co., Ltd.
[0058]
In addition, a haze value is a value calculated | required by the following formula | equation.
Haze (H) = (diffuse transmittance / total light transmittance) × 100 (%)
[0059]
4). Wear resistance evaluation
Using a Taber abrasion tester (manufactured by Toyo Seiki), using a CS-10 abrasion wheel (manufactured by Calibrase), a Taber abrasion test was performed on the surface on which the silicon oxide layer was formed under conditions of a test load of 4.9 N and 1000 revolutions. The haze value increase (ΔH) of the sample was evaluated using the magnitude.
[0060]
The haze value (increase) was measured at four points (wear wheel passing portions) separated from each other on the sample, and the average value was used as the value of the haze increase of the sample.
[0061]
As an evaluation method, when a sample is tested, a commercially available glass plate (5 mm thickness) as a control is simultaneously tested, and the test value (ΔHs) of the sample is ± of the test value (ΔHg) of the glass plate. When the value was within 15%, the sample was evaluated as having a wear resistance equivalent to that of a glass plate (evaluation ○).
[0062]
For CS-10 wear wheels, the wear wheel rubber hardness when measured according to the rubber hardness measurement method described in Japanese Industrial Standard K6301 is within a predetermined range (standard range). Was used.
The haze value of the sample was measured in an arrangement with the wear test surface facing the light detector side.
[0063]
5. Adhesion evaluation
The test was conducted in accordance with the cross-cut tape test method described in Japanese Industrial Standard K5400.
[0064]
In addition, depending on the sample, there was a phenomenon in which the silicon oxide layer spontaneously peeled off over time immediately after the formation of the silicon oxide layer, and it was not possible to fully evaluate the sample. / 100 (natural).
[0065]
[Example 1]
A flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 80.1 parts of methyl methacrylate (hereinafter abbreviated as MMA), 13 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), azobisisobutyronitrile 0.14 parts (hereinafter abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 80 parts of a copolymer (acrylic resin (I)) having a MMA / HEMA composition ratio of 90/10 (molar ratio).
[0066]
Next, 8.9 parts of acrylic resin (I) and 1.5 parts of 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole were added from 20 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone and 30 parts of 2-propanol. Then, 1.1 parts of hexamethylene diisocyanate was added to this solution so that the isocyanate group was 1.5 equivalents relative to 1 equivalent of the hydroxy group of the acrylic resin (I) at 25 ° C. The mixture was stirred for 5 minutes to prepare a primer layer forming coating solution.
[0067]
Further, 50 parts by weight of 10% strength aqueous acetic acid was added little by little to a mixed solution of 120 parts by weight of methyltrimethoxysilane and 100 parts by weight of normal propyl alcohol under ice cooling, and stirred for 30 minutes, and then at 25 ° C. for 1 hour. Subsequently, after stirring at 70 ° C. for 2 hours, 30 parts by weight of 1-methoxy-2-propanol was added and stirred at room temperature for 24 hours to prepare a coating resin A for forming a crosslinked resin layer.
[0068]
As the polymer resin substrate, a molded plate (Teijin Kasei “Panlite PC-1111”) having a thickness of 4 mm and a length and width of 200 mm × 200 mm made of a polycarbonate resin synthesized from bisphenol A and diphenyl carbonate was used.
[0069]
First, the primer layer-forming coating solution was coated on a polycarbonate substrate using a bar coater, and heat-treated at 120 ° C. for 1 hour to laminate a primer layer having a thickness of 4.3 μm.
[0070]
Next, the cross-linked resin layer-forming coating liquid A is coated on the primer layer using a bar coater, and heat-treated at 125 ° C. for 1 hour to laminate a 4.5 μm thick organic silicon cross-linked resin layer. did.
[0071]
Subsequently, the substrate was cut into a size of 110 mm square, and then set in a vacuum chamber of a sputtering apparatus provided with a quartz glass melt-formed target, and the vacuum pressure was 1 × 10. ^-3 After evacuating to Pa, Ar / O ₂ = 99: 1 mixed gas introduced, vacuum pressure 4 × 10 ^-1 Film formation was performed by a high-frequency magnetron sputtering method under conditions of Pa and a deposition rate of 0.002 μm / min, and a 4.4 μm silicon oxide layer was laminated on the crosslinked resin layer.
[0072]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0073]
[Example 2]
90 parts by weight of dicyclopentanyl diacrylate (Kyoeisha Chemical "Light Acrylate DCP-A") and 10 parts by weight of dipentaerythritol hexaacrylate (Kyoeisha Chemical "Light acrylate DPE-6E") are mixed and used as an ultraviolet absorber. 1.7 parts by weight of 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (Ciba Specialty Chemicals “Tinuvin 1577FF”), photopolymerization started Agent 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals “IRGACURE184”) 7 parts by weight, polyether-modified dimethylpolysiloxane (Toray Dow Silicone “SH28PA”) 0.05 parts by weight, normal propyl alcohol 80 parts by weight And mix, stir well Te, to prepare a crosslinked resin layer forming coating liquid B.
[0074]
On the same polycarbonate substrate as used in Example 1, the coating solution B for forming a crosslinked resin layer was coated using a bar coater, and then dried in a hot air dryer controlled at 70 ° C. for 1 minute, and 160 W / cm. Integrated high-pressure mercury lamp, total light quantity 1.2J / cm ² Then, a cross-linked resin layer having a thickness of 40 μm was laminated, and the substrate was further heat-treated for 30 minutes in a hot air drier controlled at 130 ° C., and then cut into a 110 mm square size.
[0075]
Next, this substrate was set in a vacuum apparatus equipped with an electron beam evaporation source. Position where the substrate surface is parallel to the horizontal direction, a straight line connecting the evaporation source and the center of the substrate (intersection of diagonal lines) intersects the substrate surface perpendicularly, and the distance between the evaporation source and the center of the substrate is 60 cm Was set.
[0076]
The vacuum pressure is 3 × 10 with the substrate heated to 90 ° C. ^-Four After evacuating to Pa, the substrate was naturally cooled to room temperature (about 30 ° C.). The vacuum pressure in the vacuum chamber after cooling at room temperature is 1 × 10 ^-Four Pa.
[0077]
Subsequently, quartz glass crushed particles (manufactured by High-Purity Chemical Laboratory, average particle size 2 mm) placed in a crucible of the evaporation source are heated with an electron beam to vaporize silicon dioxide, and the deposition rate is 0.3 μm / min. A silicon oxide layer having a thickness of 7.2 μm was laminated on the crosslinked resin layer.
[0078]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0079]
[Example 3]
90 parts by weight of tetraacrylate (Toa Gosei Chemical "Aronix M8030") composed of polyester diol, 10 parts by weight of dicyclopentanyl diacrylate (Kyoeisha Chemical "Light Acrylate DCP-A"), surface treatment with γ-methacryloxytrimethoxysilane 80 parts by weight of silica fine particles having an average particle diameter of 12 nm (catalyst conversion, 30% by weight isopropyl alcohol dispersion), photopolymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals “DAROCUR1173”) 5 parts by weight, polyether-modified dimethylpolysiloxane (“SH28PA” manufactured by Toray Dow Silicone) 0.12 part by weight, 1 methoxy 2-propanol 50 parts by weight Cross-linked resin layer forming coating solution C It was.
[0080]
The same polycarbonate substrate as used in Example 1 was coated with the coating solution C for forming a crosslinked resin layer using a bar coater, and then dried for 1 minute in a hot air drier controlled at 100 ° C. to obtain a 160 W / cm metal halide. Integrated light quantity 0.9J / cm by lamp ² Then, a 25 μm-thick crosslinked resin layer was laminated, and further subjected to a heat treatment for 30 minutes in a hot air drier controlled at 130 ° C., and then cut into a size of 110 mm square.
[0081]
Next, this substrate was set in a vacuum apparatus equipped with an electron beam evaporation source in the same manner as in Example 2, and the substrate was heated to 90 ° C. with a heater and the vacuum pressure was 3 × 10. ^-Four After evacuating to Pa, the substrate was naturally cooled to room temperature (about 30 ° C.). The vacuum pressure in the vacuum chamber after cooling at room temperature is 1 × 10 ^-Four Pa.
[0082]
Subsequently, quartz glass crushed particles (manufactured by High-Purity Chemical Laboratory, average particle size 2 mm) placed in a crucible of the evaporation source are heated with an electron beam to vaporize silicon dioxide, and the deposition rate is 0.3 μm / min. Then, a silicon oxide layer having a thickness of 6.2 μm was laminated on the crosslinked resin layer.
[0083]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0084]
[Example 4]
A crosslinked resin layer was laminated on the polycarbonate substrate in exactly the same manner as in Example 2, and heat treatment and cutting of the substrate were performed.
[0085]
Next, this substrate was set in a vacuum apparatus equipped with an electron beam evaporation source and a high-frequency coil (antenna), and the substrate was heated to 90 ° C. with a heater, and the vacuum pressure was 3 × 10. ^-Four After evacuating to Pa, the substrate was naturally cooled to room temperature (about 30 ° C.). The vacuum pressure in the vacuum chamber after cooling at room temperature is 1 × 10 ^-Four Pa.
[0086]
Subsequently, Ar / O is placed in the vacuum apparatus. ₂ = 99: 1 mixed gas was introduced and the vacuum pressure was 2 × 10 ^-1 After setting to Pa, a high frequency voltage of 13.56 MHz and 300 W was applied to the high frequency coil from the high frequency power source to excite plasma in the vacuum chamber.
[0087]
Subsequently, quartz glass (silicon dioxide) crushed particles (manufactured by High-Purity Chemical Laboratory, average particle size of about 2 mm) used for the evaporation source are heated by electron beam to vaporize silicon dioxide, and the vaporized silicon dioxide is the plasma. A silicon oxide layer having a film thickness of 6.5 μm was laminated on the cross-linked resin by an ion plating method of depositing on the substrate after passing through the space under a deposition rate of 0.2 μm / min.
[0088]
In this case as well, a straight line connecting the vapor deposition source and the center of the substrate (intersection of diagonal lines) intersects the substrate plane perpendicularly, and the distance is 60 cm.
[0089]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0090]
[Example 5]
In this example, a silicon oxide layer was formed by combining two processes of electron beam evaporation and sputtering.
[0091]
That is, first, a crosslinked resin layer was laminated on a polycarbonate substrate in exactly the same manner as in Example 2, followed by heat treatment and cutting of the substrate.
[0092]
Next, this substrate was set in a vacuum apparatus equipped with an electron beam evaporation source, and the substrate was heated to 90 ° C. with a heater, and the vacuum pressure was 3 × 10. ^-Four After evacuating to Pa, the substrate was naturally cooled to room temperature (about 30 ° C.). The vacuum pressure in the vacuum chamber after cooling at room temperature is 1 × 10 ^-Four Pa.
[0093]
Subsequently, crushed silica glass particles (manufactured by High Purity Chemical Laboratory, average particle size 2 mm) are heated with an electron beam to vaporize silicon dioxide, and a film is formed on the crosslinked resin layer at a deposition rate of 0.3 μm / min. A silicon oxide layer having a thickness of 0.6 μm was stacked.
[0094]
Subsequently, this substrate was set in a vacuum chamber of a sputtering apparatus provided with a quartz glass melt molded target, and a vacuum pressure of 1 × 10 ^-3 After evacuating to Pa, Ar / O ₂ = 99: 1 mixed gas introduced, vacuum pressure 4 × 10 ^-1 Film formation was performed by high-frequency magnetron sputtering under conditions of Pa and a deposition rate of 0.002 μm / min, and a 5.2 μm silicon oxide layer was laminated on the silicon oxide layer.
The total thickness of the silicon oxide layer in this example is 5.8 μm.
[0095]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0096]
[Example 6]
In this example, a silicon oxide layer was formed by using two processes of ion plating and CVD in combination.
[0097]
That is, first, a crosslinked resin layer was laminated on a polycarbonate substrate in exactly the same manner as in Example 2, followed by heat treatment and cutting of the substrate.
[0098]
Next, this substrate was set in a vacuum apparatus equipped with an electron beam evaporation source and a high-frequency coil (antenna) in the same manner as in Example 4, and the substrate was heated to 90 ° C. with a heater and the vacuum pressure was 3 × 10. ^-Four After evacuating to Pa, the substrate was naturally cooled to room temperature (about 30 ° C.). The vacuum pressure in the vacuum chamber after cooling at room temperature is 1 × 10 ^-Four Pa.
[0099]
Subsequently, a mixed gas of hexamethyldisiloxane monomer and oxygen was introduced into the vacuum apparatus, and the vacuum pressure was reduced to 1 × 10. ^-1 After setting to Pa, a high frequency voltage of 13.56 MHz and 200 W was applied to the high frequency coil from the high frequency power source to excite plasma in the vacuum chamber.
[0100]
Subsequently, quartz glass (silicon dioxide) crushed particles (manufactured by High-Purity Chemical Laboratory, average particle size of about 2 mm) used for the evaporation source are heated by electron beam to vaporize silicon dioxide, and the vaporized silicon dioxide is the plasma. By combining the ion plating method of depositing on the substrate after passing through the space and the CVD method using hexadimethylsiloxane monomer, a film thickness of 6.3 μm is formed on the crosslinked resin under the condition of a deposition rate of 0.1 μm / min. A silicon oxide layer was laminated.
[0101]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0102]
[Comparative Example 1]
In Example 2, a polymer resin laminate was prepared in exactly the same manner as in Example 2 except that the thickness of the silicon oxide film was changed to 3.3 μm.
[0103]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0104]
[Comparative Example 2]
In Example 2, after setting the substrate in a vacuum apparatus, the substrate was not evacuated and evacuated at room temperature to obtain a vacuum pressure of 5 × 10. ^-Four A polymer resin laminate was prepared in exactly the same manner as in Example 2 except that the electron beam evaporation of the silicon oxide film was started at Pa.
[0105]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0106]
[Comparative Example 3]
In Example 2, the same procedure as in Example 2 except that the substrate surface is inclined by 30 degrees with respect to the horizontal direction (however, the distance between the vapor deposition source and the center of the substrate is 60 cm as in Example 2). A polymer resin laminate was prepared. Since the substrate was tilted, the deposition rate of the silicon oxide film was 0.25 μm / min.
[0107]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0108]
[Comparative Example 4]
In Example 2, a polymer resin laminate was prepared in the same manner as in Example 2 except that a silicon oxide layer was laminated directly on a polycarbonate substrate without laminating a crosslinked resin layer.
[0109]
Table 1 shows various evaluation results for the silicon oxide layer and the polymer resin laminate prepared by the above method.
[0110]
[Comparative Example 5]
In Example 2, a polymer resin laminate was prepared in exactly the same manner as in Example 2 except that the crosslinked resin layer was formed by the following method.
[0111]
That is, 80 parts by weight of bifunctional acrylate (Nippon Kayaku “KAYARAD UX-8101”) and 20 parts by weight of dicyclopentanyl diacrylate (Kyoeisha Chemical “Light acrylate DCP-A”) using polyester diol and urethane diol as raw materials. UV absorber iso-octyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionate (trade name “Tinuvin 384, manufactured by Ciba Specialty Chemicals”) 2 ") 1.3 parts by weight, 70 parts by weight of 1 methoxy 2-propanol were mixed well under heating at 70 ° C, cooled to room temperature, and then photopolymerization initiator 2-hydroxy-2-methyl-1-phenyl-propane-1 -8 parts by weight (Ciba Specialty Chemicals “DAROCUR1173”) 0.1 parts by weight of ether-modified dimethyldisiloxane (Toray Dow Silicone “SH28PA”) and 30 parts by weight of isopropyl alcohol were mixed and stirred well to obtain a coating solution D for forming a crosslinked resin layer.
[0112]
This coating solution D for forming a crosslinked resin layer is coated on a polycarbonate substrate using a bar coater, then dried for 1 minute in a hot air drier controlled at 100 ° C., and an integrated light amount of 1.2 J / cm using a 160 W / cm metal halide lamp. ² Then, an actinic ray cured layer having a thickness of 40 μm was laminated, and further subjected to heat treatment for 30 minutes in a hot air dryer controlled at 130 ° C.
[0113]
Table 1 shows various evaluation results for the crosslinked resin layer, silicon oxide layer, and polymer resin laminate prepared by the above method.
[0114]
[Table 1]

[0115]
It is a table | surface which shows the result of evaluation evaluation of the film thickness and physical property of a crosslinked resin layer and a vapor deposition film in an Example and a comparative example, and a polymeric resin laminated body.
[0116]
【The invention's effect】
By applying the present invention to a resin molded product having low hardness and wear resistance such as polycarbonate, a polymer resin laminate having extremely excellent wear resistance can be obtained. It can be used for window materials and a wide range of other applications.
[Brief description of the drawings]
FIG. 1 is a schematic view showing the arrangement of substrates in a vacuum vapor deposition apparatus in Example 2. FIG.
2 is a schematic view showing the arrangement of substrates in a vacuum vapor deposition apparatus in Comparative Example 3. FIG.
FIG. 3 is an explanatory diagram of a load / unload curve for nanoindentation measurement.
[Explanation of symbols]
1. substrate
2. Vapor deposition source
3. Electron beam
4). substrate
5. Vapor deposition source
6). Electron beam
7). Load curve
8). Unloading curve
9. Displacement of unloading curve end point
10. Maximum displacement

Claims (7)

A polymer resin laminate in which a crosslinked resin layer having a thickness of 3 to 100 μm and a silicon oxide layer having a thickness of 4 to 25 μm are laminated in this order on at least one surface of the polymer resin substrate, The layer is a crosslinked resin layer having a Young's modulus in the range of 5 to 15 GPa when nanoindentation measurement is performed under the condition of a maximum load of 1 mN, and the silicon oxide layer has a Young's modulus in the range of 45 to 125 GPa. A polymer resin laminate comprising a silicon oxide layer having a displacement value at an end point of a load / displacement curve in a range of 0 to 40% of a maximum displacement value. As the cross-linked resin layer, an actinic ray curable resin layer having a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in a molecule or a unit repeating structure as a main component of a precursor material is used. The polymer resin laminate according to claim 1. 2. The polymer resin laminate according to claim 1, wherein a thermosetting resin layer containing a hydrolyzate of organosilicon trialkoxide as a main component of a precursor material is used as the crosslinked resin layer. As the silicon oxide layer, a silicon oxide layer formed by any one of an electron beam evaporation method, an ion plating method, a sputtering method, a chemical vapor deposition method (CVD method), or a combination of these methods should be used. The polymer resin laminate according to any one of claims 1 to 3. The polymer resin laminate according to any one of claims 1 to 4, wherein the polymer resin substrate has a thickness in the range of 1 to 20 mm. The polymer resin laminate according to any one of claims 1 to 5, wherein the polymer resin substrate is a molded substrate made of a polycarbonate resin. The window material for vehicles or buildings which contains the polymer resin laminated body in any one of Claims 1-6 as a component at least.

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