JP2011173345A - Method for manufacturing laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate which is formed of a plastic base suitable for various application requiring surface hardness, abrasion resistance, scratch resistance, transparency and/or less weight or the like. <P>SOLUTION: In the method for manufacturing the laminate formed by laminating the plastic base and a layer composed of organosiloxane composition, the layer composed of the organosiloxane composition is formed by curing with vacuum ultraviolet ray radiation under condition in which oxygen partial pressure is adjusted. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a laminate in which a plastic substrate and a layer made of an organosiloxane composition are laminated, and a laminate obtained by this production method. The laminate can be suitably used for window materials, sunroofs, building material sheets, display faceplates, and the like.

  Plastics are used in a wide range of applications because they are excellent in impact resistance, light weight, workability, and the like. In particular, transparent plastic is expected as a substitute for glass, and application to automobile window materials and the like that are difficult to scatter even if damaged by an impact such as a collision is desired. However, since plastic has lower surface hardness, abrasion resistance, scratch resistance, and the like than glass, its use has been limited.

  For the purpose of improving the surface hardness, abrasion resistance, scratch resistance and the like of the plastic substrate, a method of forming a coating film on the surface of the plastic substrate by a vapor phase method or a liquid phase method has been proposed. Examples of the vapor phase method include a method of laminating an inorganic oxide on the surface of a plastic substrate by a vacuum vapor deposition method or a chemical vapor deposition method (CVD method). Examples of the liquid phase method include a method of forming a silica film having a glassy crosslinked structure obtained by hydrolysis and dehydration condensation of alkoxysilane by a sol-gel method on the surface of a plastic substrate (for example, Non-patent document 1).

  However, in the method of forming a silica film by the sol-gel method, the silica compound is usually cured by heat, and since the thermosetting temperature is limited by the softening temperature of the plastic substrate, it takes time to cure, It was difficult to increase productivity. In addition, it is difficult to completely cure the silica film by thermosetting, and the productivity can be slightly improved even if a catalyst is used in combination, but the wear resistance of the formed cured film is still desired to be improved. It was rare.

  By the present inventors, it is possible to improve the wear resistance of the coating film by forming the silica film by the sol-gel method by irradiating with vacuum ultraviolet light. It has been proposed (see Patent Document 1). According to such a method, it is possible to cure the film in a short time, and there are advantages that the film has excellent wear resistance.

JP 2008-69262 A

M.M. S. Lee and N.C. J. et al. Jo, Coating of methyltrioxysilane-modified colloidal silica on polymer substituting for abrasion resistance, J. MoI. Sol-Gel Sci. Tech. , 24, 175-180 (2002).

However, in order to apply the laminate produced by the above method to a wider range of uses, it is desired to further improve the wear resistance.
The present invention has been made in view of the above circumstances. An object of the present invention is to provide a method for obtaining a laminate of a plastic substrate having excellent wear resistance and scratch resistance with high productivity.

  The present inventors have conducted intensive studies to solve the above problems. As a result, in a method for producing a laminate in which a plastic substrate and a layer made of an organosiloxane composition are laminated, the layer made of the organosiloxane composition is irradiated with vacuum ultraviolet light in a state where the oxygen partial pressure is adjusted. From the organosiloxane composition that has excellent abrasion resistance and scratch resistance compared to the case where it is formed by being cured by irradiation with vacuum ultraviolet light without adjusting the oxygen partial pressure by being cured. It was found that a layer to be obtained was obtained, and the present invention was reached.

That is, the first gist of the present invention is a method for producing a laminate in which a plastic substrate and a layer made of an organosiloxane composition are laminated, wherein the layer made of the organosiloxane composition has an adjusted oxygen partial pressure. It exists in the manufacturing method of the laminated body characterized by being hardened | cured and formed by the vacuum ultraviolet light irradiation in a state.
The second gist of the present invention resides in the method for producing a laminate according to the first gist, wherein the organosiloxane composition contains a hydrolyzable silicon compound derivative.
The third gist of the present invention resides in the method for producing a laminate according to the second gist, wherein the hydrolyzable silicon compound derivative is a hydrolyzate of alkoxysilane.
The fourth gist of the present invention resides in the method for producing a laminate according to the third gist, wherein the alkoxysilane is methyltriethoxysilane.
According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the organosiloxane composition contains a colloidal silica derivative having an average particle size of 1 nm to 200 nm. It exists in the manufacturing method of a laminated body.
The sixth gist of the present invention is that the oxygen partial pressure during the vacuum ultraviolet light irradiation is 1.0 × 10 ⁻³ atm or more and 5.0 × 10 ⁻¹ atm or less. It exists in the manufacturing method of the laminated body as described in any one summary.
A seventh aspect of the present invention resides in the method for manufacturing a laminate according to any one of the first to sixth aspects, wherein the plastic substrate includes a polycarbonate resin.
An eighth aspect of the present invention resides in a laminate obtained by the method for manufacturing a laminate as described in any one of the first to seventh aspects.

  In the present invention, the layer composed of the organosiloxane composition is formed by being cured by irradiation with vacuum ultraviolet light with the oxygen partial pressure adjusted. By adjusting the oxygen partial pressure, the wear resistance of the organosiloxane composition layer formed on the plastic substrate is greatly improved as compared with the case where the oxygen partial pressure when irradiating vacuum ultraviolet light is not adjusted. . Therefore, according to the present invention, a laminate of a plastic substrate having excellent wear resistance and high transparency can be obtained with high productivity. Moreover, the laminated body manufactured by this method can be applied to various uses requiring surface hardness, abrasion resistance, scratch resistance, transparency and / or lightness.

(A) is a Fourier transform infrared spectrophotometer showing the Si—CH ₃ bond amount and SiOH bond amount of the layer composed of each organosiloxane composition when the oxygen partial pressure during irradiation with vacuum ultraviolet light is changed ( (Hereinafter, it may be referred to as “FT-IR”), and (b) shows the case where the oxygen partial pressure during the vacuum ultraviolet light irradiation is changed and the case where the vacuum ultraviolet light irradiation is not performed. is a graph showing the relative amount of residual Si-CH ₃ bond and SiOH bonds. It is a schematic sectional drawing which shows an example of the vacuum ultraviolet light irradiation apparatus used for this invention. It is a graph which shows the change of the abrasion resistance of the layer which consists of an organosiloxane composition when oxygen partial pressure is changed in the manufacturing method of the laminated body of this invention. In the manufacturing method of the laminated body of this invention, it is a graph which shows the relationship between oxygen partial pressure, the abrasion resistance of the layer which consists of organosiloxane compositions, and the irradiation intensity | strength of vacuum ultraviolet light. In the manufacturing method of the laminated body of this invention, it is a graph which shows the relationship between the oxygen partial pressure on the conditions which made irradiation total light quantity constant, and the abrasion resistance of the layer which consists of organosiloxane compositions.

  Hereinafter, the present invention will be described in detail with reference to embodiments, examples, and the like, but the present invention is not limited to the following embodiments, examples, and the like, and does not depart from the gist of the present invention. Any change can be made.

[1. Overview]
The method for producing a laminate of the present invention is a method for producing a laminate comprising a plastic substrate and a layer comprising an organosiloxane composition cured by irradiating vacuum ultraviolet light in a state where the oxygen partial pressure is adjusted. is there. The method for producing a laminate of the present invention comprises a step in which a layer comprising the organosiloxane composition is formed by being cured by irradiation with vacuum ultraviolet light in a state where the oxygen partial pressure is adjusted (hereinafter, this step is referred to as “organosiloxane composition”). In some cases, a different step may be included before and / or after the curing step of the layer made of the organosiloxane composition. Alternatively, the coating of the organosiloxane composition and the curing step of the layer made of the organosiloxane composition may be performed a plurality of times to increase the thickness of the layer made of the organosiloxane composition.

In the present invention, the layer made of the organosiloxane composition is formed by being cured by irradiation with vacuum ultraviolet light while adjusting the oxygen partial pressure, thereby improving the wear resistance of the layer made of the organosiloxane composition. The reason is not clear, but can be estimated as follows.
In FIG. 1 (a), the oxygen partial pressure at the time of vacuum ultraviolet light irradiation with respect to a layer made of an organosiloxane composition containing methyltriethoxysilane (materials, film forming conditions, etc. are the same as those in the example) was changed. cases, the measurement results of FT-IR showing the binding amount of Si-CH ₃ groups and SiOH groups of the membrane surface made of the organosiloxane composition. FIG. 1B shows the relative residual amounts of Si—CH ₃ groups and SiOH groups obtained from FIG. As apparent from FIGS. 1 (a) and (b), the amounts of Si—CH ₃ groups and SiOH groups derived from the organosiloxane composition were significantly reduced by irradiation with vacuum ultraviolet light. The oxygen partial pressure concentration was not significantly affected. Therefore, the improvement in wear resistance is not accompanied by a large change in the chemical structure such as Si—CH ₃ group and SiOH group, but is generated by, for example, irradiation of oxygen molecules entering the film from the gas phase or vacuum ultraviolet light irradiation. It is thought that this is caused by a very small amount of active oxygen species such as O ₃ . It is speculated that these oxygen molecules or reactive oxygen species accelerate structural changes that could not be realized in vacuum ultraviolet without oxygen introduction, such as further cross-linking of the film.

In addition, the measurement of FT-IR in the said FIG. 1 is a Fourier-transform infrared spectroscopy apparatus (Fourier-transform Infrared Spectroscopy: FT-IR, Shimadzu Corporation "FT-IR 8400S"), and a horizontal total reflection absorption measurement. Using an apparatus (“ATR-8200HA” manufactured by Shimadzu Corporation), the measurement was performed by attenuated total reflection spectroscopy (ATR spectroscopy). In the measurement of the layer composed of the organosiloxane composition, the film was brought into contact with the ZnSe solid prism, the pressure plate was lowered so that the layer composed of the organosiloxane composition and the prism were in close contact, and then the infrared light was applied to the prism. Was irradiated. The measurement range and the number of integrations are as follows.
Wave number range: 4000 to 700 cm ⁻¹
Integration count: 40times

[2. Plastic substrate]
The material of the plastic substrate according to the present invention is not particularly limited as long as the effects and objects of the present invention are not impaired, and various resins or substrates containing them as components are preferably used.

  Specific examples of the resin constituting the plastic substrate include thermoplastic resins such as polycarbonate resin, polyester resin, acrylic resin, polyolefin resin, polyether resin, polyamide resin, vinyl resin, and cellulose resin; allyl resin, Examples thereof include thermosetting resins such as urethane resins and epoxy resins. One kind of these resins may be used alone, or two or more kinds of resins may be used in any ratio and combination.

  Among the above-mentioned various resins, in particular, the polycarbonate resin has advantages such as excellent transparency and workability, light weight and high toughness, so various vehicle uses such as window materials for automobiles, cover materials for headlights, etc. The plastic substrate according to the present invention can be used for a wide range of applications such as optical applications such as lenses such as eyeglasses, and the laminate according to the present invention is expected to greatly improve compared to the prior art. Polycarbonate resin is preferred. The proportion of the polycarbonate resin in the plastic substrate when the plastic substrate contains a component other than the polycarbonate resin is preferably 50 from the viewpoint of the rigidity, surface hardness and heat distortion resistance (load deflection temperature) of the plastic substrate. % By weight or more, more preferably 70% by weight or more.

  The polycarbonate resin is a copolymer produced by a reaction between bisphenols and carbonates.

  Examples of bisphenols include “Bisphenol A”, “Bisphenol C”, “Bisphenol E”, “Bisphenol F”, “Bisphenol M”, “Bisphenol P”, “Bisphenol S”, “ Bisphenol Z "and the like. Of these, “bisphenol A” and “bisphenol Z” (in which the central carbon participates in the cyclohexane ring) are preferable, and “bisphenol A” is particularly preferable because of easy industrial availability. Examples of the carbonic acid esters include bisalkyl carbonate, bisaryl carbonate, and phosgene. The polycarbonate resin may be only one kind of resin, two or more kinds of polymer blends, or a copolymer of plural kinds of monomers.

  The polycarbonate resin may be a polycarbonate-based polymer alloy containing a polycarbonate resin or a resin in which a resin other than the polycarbonate resin is blended with the polycarbonate resin. Examples other than the polycarbonate resin include polycondensates of cyclohexanedimethanol and cyclohexanedicarboxylic acid, which are alicyclic polyesters, and polyarylate resins. In addition, as copolymerization components for making aromatic polyester carbonates, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid or derivatives thereof (for example, aromatic dicarboxylic acid diesters, aromatic dicarboxylic acid chlorides) are included. It may be.

  There is no restriction | limiting in particular in the manufacturing method of polycarbonate resin. For example, (a) using an alkali metal salt of bisphenols and a carbonic acid ester derivative (for example, phosgene) active for nucleophilic attack as a raw material, at the interface between an organic solvent (for example, methylene chloride, etc.) that dissolves the produced polymer and alkaline water Interfacial polymerization method in which polycondensation reaction is performed, (b) Pyridine method in which polycondensation reaction is carried out in an organic base such as pyridine using bisphenols and a carbonic acid ester derivative active in nucleophilic attack as raw materials, and (c) Bisphenols and bis A melt polymerization method in which a carbonic acid ester (preferably diphenyl carbonate) such as alkyl carbonate or bisaryl carbonate is used as a raw material, and melt polycondensation, (d) a method of producing by reaction of bisphenols with carbon monoxide or carbon dioxide, etc. Polycarbonate resins produced by any known method can be used.

  Although there is no restriction | limiting in particular in the molecular weight of polycarbonate resin, The weight average molecular weight Mw (single molecular weight dispersion | distribution polystyrene conversion) measured by the gel permeation chromatography (henceforth "GPC") using a 40 degreeC chloroform solvent is. From the viewpoint of impact strength and stress crack prevention, 15,000 or more is preferable, and 20,000 or more is particularly preferable. On the other hand, from the viewpoint of improving melt fluidity and improving moldability, 500,000 or less is preferable, and 200,000 or less is particularly preferable.

  The plastic base material appropriately contains various additives such as heat stabilizers, ultraviolet absorbers, plasticizers, lubricants, mold release agents, pigments, antistatic agents, impact resistance improvers, and / or fillers. May be. These may be used alone or in combinations of two or more in any ratio and combination. Examples of the heat stabilizer include phosphite-based heat stabilizers such as tris (2,4-di-tert-butylphenyl) phosphite (“MARK2112” manufactured by Asahi Denka Co., Ltd.) and the like. In addition, as a stabilizer that may be added for the purpose of improving the thermal stability at the time of molding, hindered phenolic phosphorus compounds (“Irganox 1010”, “Irganox 1076”, etc., manufactured by Ciba Geigy Co., Ltd.), partial Examples thereof include acrylated polyphenol-based phosphorus compounds (“SUMILIZER GS,“ SUMILIZER GM ”, etc.” manufactured by Sumitomo Chemical Co., Ltd.), phosphite-based phosphorus compounds (“Irgaphos 168” manufactured by Ciba Geigy Corporation), and the like. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers. Examples of the impact resistance improver include elastomers and rubbers. Examples of other additives include long-chain aliphatic alcohols and long-chain aliphatic esters.

  When components other than resin are contained in the plastic substrate, the ratio of the resin in the plastic substrate is from the point of impact resistance, rigidity, surface hardness and heat distortion resistance (deflection temperature under load) of the plastic substrate. 50 weight% or more is preferable and 70 weight% or more is especially preferable.

  There is no restriction | limiting in particular about the shape of a plastic base material. Plastics of various shapes such as various plastic moldings such as two-dimensional structures such as films and sheets and three-dimensional structures can be used as the plastic substrate. The thickness of the plastic substrate may be any thickness depending on the use of the plastic resin laminate, but is preferably 100 μm or more, and particularly preferably 300 μm or more from the viewpoint of securing the substrate strength. On the other hand, from the viewpoint of making the thickness of the molded product uniform and facilitating processing, it is preferably 20 mm or less, and particularly preferably 10 mm or less.

  There are no particular restrictions on the method for producing the plastic substrate. For example, injection molding, extrusion molding, hot press molding, vacuum press molding, blow molding, compression molding, injection compression molding, solution casting, plate molding A plastic substrate manufactured by a known method such as punching can be used.

  The light transmittance of the plastic substrate is preferably higher when applied to alternative uses such as glass. Specifically, 70% or more is preferable, and 75% or more is particularly preferable. The light transmittance measurement method can be the same as the method described in the examples.

  The surface of the plastic substrate may be subjected to activation treatment such as flame oxidation treatment (frame treatment), corona treatment, plasma treatment, primer treatment, and the like. Further, the surface of the plastic substrate may be washed (degreased, etc.) with a solvent such as alcohol before laminating the layer made of the organosiloxane composition.

[3. Layer comprising an organosiloxane composition]
The layer made of the organosiloxane composition according to the present invention may be a layer formed by being cured by irradiation with vacuum ultraviolet light in a state where the oxygen partial pressure is adjusted.
For the production of a layer made of an organosiloxane composition (production of a cured film), a layer made of an organosiloxane composition may be directly formed on a plastic substrate, or from a previously prepared organosiloxane composition. The film to be formed may be laminated on a plastic substrate, but the former is preferable from the viewpoint of easy operation.

In addition, the laminate obtained by the method for producing a laminate of the present invention has a plastic substrate and an organosiloxane composition according to the present invention as long as the plastic substrate and a layer made of the organosiloxane composition according to the present invention are laminated. Another layer may be formed between and / or outside the layer made of the object.
Specific examples of the method for forming a layer composed of an organosiloxane composition include a method in which an organosiloxane composition (before curing) is applied on a substrate and then cured.

(Preparation of organosiloxane composition before curing)
As the organosiloxane composition contained in the layer composed of the organosiloxane composition, a composition containing a hydrolyzable silicon compound derivative is preferable, and in addition, a colloidal silica derivative or the like may be contained. As a method of forming a layer comprising an organosiloxane composition, a hydrolyzable silicon compound produced by applying an organosiloxane composition containing a hydrolyzable silicon compound on a substrate and then hydrolyzing the hydrolyzable silicon compound A method of curing the derivative is particularly preferred. Hereinafter, the method of curing a hydrolyzable silicon compound derivative produced by applying a hydrolyzable silicon compound on the substrate and then hydrolyzing it will be described, but the present invention is limited to this. It is not a thing.

Hydrolyzable silicon compound The hydrolyzable silicon compound is a silicon-containing compound having a hydrolyzable group or hydroxyl group directly bonded to a silicon atom, and the hydrolyzable silicon compound derivative is a hydrolyzable silicon compound. This is what you get. Here, when hydrolyzing a hydrolyzable silicon compound, the hydrolyzate produced may be further condensed. Therefore, the “hydrolyzable silicon compound derivative” usually includes hydrolysis of the hydrolyzable silicon compound. In addition to the product, an unreacted product of the hydrolyzable silicon compound and a condensate of the hydrolyzate are included. From the viewpoint of easy availability and handling, the silicon-containing compound having a hydrolyzable group directly bonded to a silicon atom is preferably an alkoxysilane, and particularly preferably an alkoxysilane represented by the following formula (I).
_{^{R 1 m R 2 n Si (}} OR 3) 4-m-n ... (I)
(In the formula, R ¹ and R ² are each one or more selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, vinyl or (meth) acryloyl group, amino group, glycidyl group and 3,4-epoxycyclohexyl group). R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m and n are integers of 0 to 2, and m + n is 0 to 0. 2)

  Specific examples of the alkoxysilane represented by the formula (I) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltripropoxy Silane, methyltriisopropenoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriacetoxysilane, vinyltriisopropenoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ Chloropropyltripropoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meta ) Acrylyloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane Dimethyldiethoxysilane, phenylmethyldiethoxysilane, diphenyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycid Xylpropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxy Silane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ- Lucaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, etc. Can be mentioned.

  Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and the like are preferable, and methyltriethoxysilane is more preferable because a layer having excellent wear resistance can be easily obtained. Only one type of alkoxysilane may be used, or two or more types may be used in any ratio and combination. In particular, when a layer composed of an organosiloxane composition is produced by the formation method described later, it is preferable that the organosiloxane composition contains 30% by weight or more of alkoxysilane having n of 1 in the above formula (I). % Or more is particularly preferable.

(Colloidal silica)
Colloidal silica is usually submicron sized silica (SiO ₂ ) particles.
The average particle size of colloidal silica is preferably larger from the viewpoint of the stability of the composition comprising the organosiloxane composition, and on the other hand, it is preferably smaller from the viewpoint of ensuring the transparency of the layer comprising the organosiloxane composition. . Specifically, the average particle diameter of colloidal silica is preferably 1 nm or more, particularly preferably 2 nm or more, and on the other hand, 200 nm or less is preferable, 100 nm or less is more preferable, and 50 nm or less is particularly preferable. The average particle diameter of colloidal silica can be determined by observation with a scanning electron microscope (hereinafter referred to as SEM). In addition, when the particle diameter is described in a catalog or the like, the numerical value can be substituted.

As the colloidal silica, those dispersed in a dispersion medium can be used. Examples of the dispersion medium include water, an organic solvent, a mixed solvent of water and a hydrophilic organic solvent, and the like. Examples of the hydrophilic organic solvent include aliphatic alcohols having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene acetate Examples include ethylene glycol derivatives such as glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; diacetone alcohol, dimethylacetamide, and xylene. Among these, water or a mixed solvent of water and an aliphatic alcohol having 1 to 4 carbon atoms is preferable from the viewpoint of dispersion stability and ease of drying of the dispersion medium, and water and a fatty acid having 1 to 4 carbon atoms. Among mixed solvents with aliphatic alcohols, a mixed solvent of water and an aliphatic alcohol having 1 to 3 carbon atoms is particularly preferable.
The concentration of colloidal silica in the dispersion medium is preferably 10% by weight or more and 50% by weight or less.

Commercially available colloidal silica is available from, for example, DuPont Co., Ltd., Nalco Chemical Company, Nissan Chemical Industries, Ltd., and Catalytic Chemical Industry Co., Ltd. Specific examples of colloidal silica that may be used in the organosiloxane composition according to the present invention include “LUDOX LS” manufactured by Du Pont Co., Ltd., “Nalcoag 1034A” manufactured by Nalco Chemical Company, Nissan Chemical Co., Ltd. “Snowtex 30”, “Snowtex 40”, “Snowtex O”, “MA-ST”, “IPA-ST”, “NBA-ST”, “IBAST”, “EG-ST”, “XBA-” ST "," NPC-ST "and" DMAC-ST "," Cataloid S30 "and" Cataloid S40 "manufactured by Catalytic Chemical Industry Co., Ltd. The characteristics of the colloidal silica mentioned here will be described. “LUDOX LS” has about 30 wt% SiO ₂ dispersed in water. “Nalcoag 1034A” has about 34 wt% SiO ₂ dispersed in water, a low Na ₂ O content, and a pH of about 3.1. “Snowtex 30”, “Snowtex 40”, “Cataloid S30” and “Cataloid S40” have SiO ₂ dispersed in a basic aqueous solution. “Snowtex O” has SiO ₂ dispersed in an acidic aqueous solution. “MA-ST”, “IPA-ST”, “NBA-ST”, “IBAST”, “EG-ST”, “XBA-ST”, “NPC-ST” and “DMAC-ST” are in an organic solvent. In this case, SiO ₂ is dispersed. These may use only 1 type, or may use 2 or more types by arbitrary ratios and combinations.

  When alkoxysilane and colloidal silica are used, the composition ratio of alkoxysilane and colloidal silica is such that the wear resistance performance of the layer made of the organosiloxane composition obtained with more colloidal silica and cracking due to shrinkage during curing occurs. On the other hand, less colloidal silica is preferable from the viewpoint of the coating property of the organosiloxane composition before curing, and the transparency of the layer made of the resulting organosiloxane composition. Specifically, the weight ratio in terms of solid matter with respect to the total amount of alkoxysilane and colloidal silica, the alkoxysilane is preferably 20% or more, more preferably 25% or more, It is preferably 95% or less, and more preferably 90% or less.

-Water Applying a hydrolyzable silicon compound on a substrate and then hydrolyzing it to cure a "hydrolyzable silicon compound derivative" to form a layer comprising the organosiloxane composition according to the present invention. In this case, it is preferable that water necessary for hydrolysis is mixed with a hydrolyzable silicon compound in an amount necessary for smooth progress of curing (hydrolysis and subsequent polycondensation). May be reacted. The amount of water used for the hydrolysis is preferably 0.5 times mol or more and particularly preferably 1 time mol or more based on the hydrolyzable silicon compound. On the other hand, 50 times mole or less is preferable and 30 times mole or less is especially preferable.

When alkoxysilane and colloidal silica coexist, alkoxysilane itself hydrolyzes in the presence of water, and reacts with OH groups on the surface of colloidal silica to cohydrolyze. When the alkoxysilane and colloidal silica cohydrolyzed are irradiated with vacuum ultraviolet light, these components are polycondensed and cured. Therefore, when using alkoxysilane and colloidal silica, it is preferable to select those having the same hydrolysis rate so that they can be co-hydrolyzed. In general, as the carbon number of the alkyl group of the hydrolyzable silicon compound (for example, the group represented by R ² in the alkoxysilane represented by the formula (I)) increases, the hydrolysis rate decreases. Therefore, a hydrolyzable silicon compound having a suitable hydrolysis rate may be selected according to the hydrolysis rate of colloidal silica.

-Catalyst Although the hydrolysis reaction may be performed in the presence of a catalyst or in the absence of a catalyst, it is preferably performed in the presence of a catalyst in terms of the reaction rate. There is no restriction | limiting in particular as a hydrolysis catalyst, unless the effect of this invention is impaired. Specifically, for example, inorganic acid catalysts such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid Organic acid catalysts such as p-toluenesulfonic acid; quaternary ammonium salts of the inorganic acids or organic acids; amine salts of the inorganic acids or organic acids such as trimethylamine and n-butylamine; organotin compounds, organoaluminum compounds, etc. And organic metal compounds and organic acid metal salts. Of these, hydrochloric acid, acetic acid, or quaternary ammonium salts thereof are preferable from the viewpoint of controlling the reaction rate. These catalysts may be used alone or in combinations of two or more in any ratio and combination.

  The amount used in the case of using a catalyst is preferably 0.001 mol% or more based on the amount of hydrolyzable group (for example, alkoxysilyl group of alkoxysilane) in the hydrolyzable silicon compound to be used. It is more preferable to set it as mol% or more, and on the other hand, 10 mol% or less is preferable and 5 mol% or less is especially preferable.

  The conditions for the hydrolytic condensation reaction may be selected from known conditions. The conditions for the hydrolytic condensation reaction vary depending on the type and amount of the hydrolyzable silicon compound, the type of the dispersion medium, etc., but the temperature at the start of hydrolysis or polycondensation is usually about room temperature, You may heat or cool as needed.

Others The composition containing the hydrolyzable silicon compound (before hydrolysis) may contain a diluting solvent from the viewpoint of allowing the reaction to proceed smoothly. When colloidal silica is used in combination and hydrolysis is performed after mixing alkoxysilane and colloidal silica, if the dispersion medium is used in colloidal silica, the dispersion medium can be applied as all or part of the diluent solvent. Examples of the diluent solvent include lower alcohols such as methanol, ethanol, propanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; diols such as ethylene glycol; ethylene glycol monomethyl ether And the like. Of these, lower alcohols are preferred from the viewpoint that the hydrolysis reaction of the hydrolyzable silicon compound easily proceeds smoothly. When using a diluting solvent, one type may be used alone, or two or more types may be used in any ratio and combination.

The organosiloxane composition before curing according to the present invention may contain other components in addition to the above-described components depending on the application and the like, as long as the effects and objects of the present invention are not impaired. Other components include various modifiers such as zinc oxide, alumina, titanium oxide, cerium oxide, tin oxide, antimony oxide, and iron oxide; pigments, ultraviolet absorbers, antioxidants, flame retardants, fillers, leveling agents And surfactants. Other components may be used alone or in combination of two or more in any ratio and combination.
When the above-described other components are contained in the organosiloxane composition before curing according to the present invention, the organosiloxane contained in the organosiloxane composition before curing exhibits the excellent effect of the present invention. From the easy point, 50 weight% or more is preferable and it is especially preferable that it is 80 weight% or more.

  The method for preparing the organosiloxane composition (before curing) is not particularly limited. Specifically, for example, when alkoxysilane is used as the hydrolyzable silicon compound of the organosiloxane composition and colloidal silica is used in combination, a mixture of a hydrolysis catalyst and water and a dilution solvent are mixed with alkoxysilane, and a few minutes to several Examples of the method include mixing the colloidal silica after stirring for a period of time. Here, the mixing order of alkoxysilane and colloidal silica may be reversed, or after mixing alkoxysilane and colloidal silica, a mixture of hydrolysis catalyst and water and a diluting solvent may be mixed. Moreover, as shown in the below-mentioned Example, after mixing the alkoxysilane, the colloidal silica, and the aqueous solution of a hydrolysis catalyst, you may mix a dilution solvent.

(Application)
In the method of forming a layer comprising an organosiloxane composition according to the present invention, the organosiloxane composition (before curing) prepared as described above is usually applied on a plastic substrate and then vacuum ultraviolet light is applied thereto. Is cured by irradiation. There is no restriction | limiting in particular in a coating method, It can apply | coat on a base material by various well-known coating methods. Specific examples of the coating method include brush coating, bar coater, spray coater, roll coater, flow coater, spin coater, centrifugal coater coating, dip coating, and screen process.

  The coating liquid applied on the plastic substrate may be left in the air and air-dried or heated and dried as necessary. The heating method in the case of heating is not particularly limited, and can be performed using, for example, an infrared heater, an oven, or the like. The heating temperature is preferably higher from the viewpoint of work efficiency, and on the other hand, it is preferably lower from the viewpoint of reducing damage to the plastic substrate. Specifically, it is preferably 40 ° C. or higher, particularly preferably 60 ° C. or higher. On the other hand, it is preferably 120 ° C. or lower, and preferably 100 ° C. or lower. Since the curing reaction is performed by vacuum ultraviolet light, the drying time is sufficient if the solvent can be removed. However, the present invention does not exclude that a curing reaction is caused to some extent by heat and then cured by irradiation with vacuum ultraviolet light. Specifically, the drying time is preferably several minutes or more, and preferably 1 hour or less.

(Vacuum ultraviolet light irradiation)
In the method for forming a layer made of the organosiloxane composition according to the present invention, the layer made of the organosiloxane composition is cured by irradiation with vacuum ultraviolet light with the oxygen partial pressure adjusted. That is, by applying vacuum ultraviolet light while adjusting the oxygen partial pressure, the hydrolyzate of the hydrolyzable silicon compound in the organosiloxane composition before curing or the co-hydrolysis of the hydrolyzable silicon compound and colloidal silica. It is considered that the film can be cured by condensation polymerization of the decomposition product.

  In the present invention, vacuum ultraviolet light refers to light having a wavelength range of 15 nm to 200 nm. The light source for vacuum ultraviolet light is not particularly limited as long as it generates light in the wavelength range. Specific examples include an excimer lamp, an excimer laser, a deuterium lamp, and a metal halide lamp. A mercury discharge lamp that emits light having a wavelength of 185 nm or the like can also be used.

Among the above, a rare gas excimer lamp that uses excimer light emission by a rare gas because the wavelength range to be radiated is concentrated on one wavelength so that the efficiency is high and a high output is obtained in the vacuum ultraviolet wavelength range. And Xe ₂ excimer light (oscillation wavelength 172 nm), Kr ₂ excimer light (146 nm), Ar ₂ excimer light (126 nm), and the like are more preferable. Among them, the excimer lamp is particularly preferable because it can obtain a high output of several tens of mW per unit area, and can be continuously irradiated and instantaneously turned on and off, and the wavelength range of 160 nm to 200 nm is preferable because of its transparency to silica. Xe ₂ excimer lamp is most preferable.

The irradiation intensity of vacuum ultraviolet light is preferably higher in terms of easy curing of the organosiloxane composition in a short time, but is preferably lower in terms of uniformity of the layer formed of the organosiloxane composition to be formed. Specifically, it is preferably at 5MWcm ^-2 or more, particularly preferably at 10MWcm ^-2 or more, while, preferably at 100 mWcm ^-2 or less, particularly preferably not more 70MWcm ^-2 or less . In addition, the said irradiation intensity is converted into the value measured in the position of the organosiloxane composition hardened | cured in a vacuum ultraviolet light irradiation apparatus with a vacuum ultraviolet light meter ("H8025-172 / C8026" by Hamamatsu Photonics Co., Ltd.). It is the value.

  The irradiation time of vacuum ultraviolet light is preferably shorter in terms of productivity, but longer in terms of wear resistance and uniformity of the layer formed of the organosiloxane composition to be formed. Specifically, it is preferably 5 seconds or more, particularly preferably 15 seconds or more, and on the other hand, it is preferably 30 minutes or less, and particularly preferably 10 minutes or less.

The atmosphere at the time of vacuum ultraviolet light irradiation contains a very small amount of oxygen. Further, the atmosphere at the time of irradiation with vacuum ultraviolet light may include any atmosphere other than oxygen as long as it does not hinder the curing of the organosiloxane composition by irradiation with vacuum ultraviolet light. From the estimation mechanism of the reason for improving the abrasion resistance of the layer made of the composition, a very small amount of oxygen molecules are taken into the film, or a very small amount of active oxygen species such as O ₃ is generated by irradiation with vacuum ultraviolet light. It is considered that an atmosphere that does not interfere with the above is preferable. Examples of such atmospheres other than oxygen include inert gases such as nitrogen and rare gases. Of the inert gases, nitrogen gas or argon gas is preferable from the viewpoint of cost and the like, more preferably nitrogen gas, and the atmosphere at the time of vacuum ultraviolet light irradiation is particularly preferably an atmosphere in which air is diluted with an inert gas. .

  The irradiation with vacuum ultraviolet light is performed in a state where the oxygen partial pressure in the atmosphere is adjusted. The method for adjusting the oxygen partial pressure is not particularly limited as long as the oxygen partial pressure in the irradiation region of vacuum ultraviolet light can be adjusted. A preferred example of the atmosphere during irradiation with vacuum ultraviolet light will be described with reference to the drawings. For example, when vacuum ultraviolet light irradiation is performed by a vacuum ultraviolet light irradiation apparatus 10 as shown in FIG. 2, the inert gas 1 and the air 2 whose flow rates are adjusted by a flow meter are mixed and then the vacuum ultraviolet light irradiation apparatus. The inert gas 1 and the air 2 each having a flow rate adjusted by a flow meter may be directly introduced into the vacuum ultraviolet light irradiation apparatus 10. In the vacuum ultraviolet light irradiation apparatus 10 in FIG. 2, the organosiloxane composition 3 to be cured is irradiated with vacuum ultraviolet light from the light source 4 with the oxygen partial pressure adjusted. In the vacuum ultraviolet light irradiation apparatus 10, the distance between the organosiloxane composition 3 to be cured and the light source 4 can be appropriately adjusted by the sample stage 5.

The oxygen partial pressure in the atmosphere at the time of irradiation with vacuum ultraviolet light is preferably higher from the viewpoint of easy incorporation of oxygen molecules into the film and ease of generation by irradiation with vacuum ultraviolet light such as active oxygen species such as O _3. it is conceivable that. On the other hand, it is preferable that the oxygen partial pressure is low from the viewpoint that absorption of vacuum ultraviolet light by oxygen hardly occurs. Regarding the absorption of vacuum ultraviolet light by oxygen, the longer the distance between the light source of vacuum ultraviolet light and the organosiloxane composition to be cured, the greater the decrease in the intensity of vacuum ultraviolet light due to absorption. Accordingly, the oxygen partial pressure in the atmosphere at the time of irradiation with vacuum ultraviolet light is preferably adjusted as appropriate according to the distance between the light source of vacuum ultraviolet light and the organosiloxane composition to be cured. It is preferable to adjust the partial pressure higher.

The distance between the vacuum ultraviolet light source and the organosiloxane composition to be cured is preferably short in view of the fact that the absorption of vacuum ultraviolet light by oxygen hardly occurs and the apparatus is compact, and on the other hand, oxygen molecules into the film are preferred. It is presumed that the longer one is preferable from the viewpoint of easiness of generation by vacuum ultraviolet light irradiation such as active oxygen species such as O _{3 and the} like. The distance between the vacuum ultraviolet light source and the organosiloxane composition to be cured is preferably 0.1 cm or more, more preferably 0.5 cm or more, and on the other hand, 5.0 cm or less. Preferably, it is 2.0 cm or less.

  In addition, the preferable range of the oxygen partial pressure in the atmosphere at the time of irradiation with vacuum ultraviolet light varies depending on the composition of the organosiloxane composition to be cured, particularly the kind of the organosiloxane, and therefore, it is preferable to adjust accordingly. .

For the reasons described above, the oxygen partial pressure in the atmosphere at the time of irradiation with vacuum ultraviolet light is specifically preferably less than the oxygen partial pressure in the atmosphere, and is preferably 5.0 × 10 ⁻¹ atm or less. More preferably, it is 1.0 × 10 ⁻¹ atm or less, more preferably 5.0 × 10 ⁻² atm or less, and on the other hand, 1.0 × 10 ⁻³ atm or more. Is preferably 3.0 × 10 ⁻³ atm or more, and more preferably 5.0 × 10 ⁻³ atm or more. By setting it within the above range, it becomes possible to obtain a layer made of an organosiloxane composition having very good wear resistance. Note that. The oxygen partial pressure is calculated based on the supply amount of each gas supplied into the vacuum ultraviolet light irradiation apparatus.
Here, the oxygen partial pressure may be changed over time, but is preferably constant in terms of the uniformity of the layer formed of the organosiloxane composition to be formed.

[4. Layer thickness of organosiloxane composition]
The thickness of the layer made of the organosiloxane composition according to the present invention is preferably thicker from the viewpoint of uniformity of the thickness of the layer made of the organosiloxane composition and improvement in wear resistance of the plastic substrate. Is preferable in that it is sufficiently cured by vacuum ultraviolet light and cracks are unlikely to occur in the layer made of the organosiloxane composition. Specifically, the thickness of the layer made of the organosiloxane composition according to the present invention is preferably 0.5 μm or more, particularly preferably 2 μm or more, and preferably 20 μm or less. The thickness is particularly preferably 10 μm or less.

The thickness of the layer composed of the organosiloxane composition can be easily calculated from the interference of light reflected at the interface between the upper surface and the lower surface of the film.
In addition, when the thickness of the layer composed of the target organosiloxane composition is thick, the target film thickness can be achieved by applying the organosiloxane composition and curing the layer composed of the organosiloxane composition multiple times. preferable.

[5. Application]
Since the laminate of the present invention can be suitable for various uses that require surface hardness, abrasion resistance, scratch resistance, transparency and / or lightness, for example, window materials, headlights, etc. Various vehicle applications such as automobiles such as automobile cover materials, roofing materials, etc .; civil engineering and architectural applications such as window glass, outer wall materials, windshield glass, road noise barriers, etc .; It is expected that it can be used for a wide range of applications such as optical applications such as lenses.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof. In addition, the evaluation method used by the Example and the comparative example is as showing below.

[Light transmittance]
The light transmittance in wavelength 400-830 nm was measured using the ultraviolet visible spectrophotometer ("V-550" by JASCO Corporation). The measurement conditions are as follows.
Wavelength range: 830 nm to 400 nm
Response: medium
Band width: 0.2 nm
Scanning speed: 200 nm · min ⁻¹
Data capture interval: 0.5 nm

[Abrasion resistance]
Steel wool # 0000 was attached to a plane friction tester manufactured by Coating Tester Kogyo Co., Ltd., and was worn at a load of 9.8 N · cm ² , and the light transmittance after wear was measured every certain number of times to evaluate the wear resistance. .

[FT-IR measurement]
The FT-IR measurement is performed using a Fourier transform infrared spectrometer (“FT-IR 8400S” manufactured by Shimadzu Corporation) and a horizontal total reflection absorption measuring apparatus (“ATR-8200HA” manufactured by Shimadzu Corporation). This was performed by attenuated total reflection spectroscopy. Specifically, in the measurement of a layer composed of an organosiloxane composition, the film was brought into contact with a ZnSe solid prism, and after the pressure plate was lowered so that the layer composed of the organosiloxane composition and the prism were in close contact with each other. The prism was irradiated with infrared light. The measurement range and the number of integrations were as follows.
Wave number range: 4000 to 700 cm ⁻¹
Integration count: 40times

[Example]
(Preparation of organosiloxane composition)
In a ^three- necked flask (200 cm ³ ), methyltriethoxysilane (MTES (CH ₃ Si (OC ₂ H ₅ ) ₃ manufactured by Aldrich, purity 99% by weight)) so that the weight ratio of the SiO ₂ component is 1: 1. 00 cm ³ , colloidal silica (LUDOX (registered trademark) LS, Aldrich® LS, purity 30 wt%) 16.44 cm ³ was mixed dropwise by an autopipette, and acetic acid (manufactured by Wako Pure Chemical Industries, purity 99.7 wt. %) was 2.00 cm ³ addition, after the addition of purified water 24.00Cm ^3, stirred with a stirrer, and reacted for 24 hours at room temperature.
To the solution after the reaction, 80 cm ³ of ethanol was mixed as an azeotropic solvent. While stirring under reduced pressure using a rotary pump equipped with a trap (“N820.3FT.18” manufactured by KNF NEUBERGER, ultimate pressure 0.8 kPa [abs.]), The flask was heated at 50 ° C. or lower with a water bath, Water and ethanol remaining therein were removed, and concentration was performed until the yield reached 20.0 g to obtain a silane sol.
The obtained silane sol was weighed with isobutyl alcohol (manufactured by Wako Pure Chemicals, purity 99.5% by weight) and 2-ethoxyethanol (manufactured by Wako Pure Chemicals, purity 99% by weight) so that the silane sol concentration was 40% by weight. A solution having a ratio of 1: 1 was mixed, and further, 2.00 cm ^{3 of} tetramethylammonium formate (manufactured by Aldrich, 25% by weight aqueous solution) added as a curing catalyst was transferred to a sample bottle and stored in a freezer.

(Application of organosiloxane composition)
A polycarbonate resin substrate (Iupilon (registered trademark) sheet NF-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) having a thickness of 0.5 mm was cut into a 30 mm × 30 mm short plate shape. The organosiloxane composition solution stored in the refrigerator was separated into a plastic syringe, and a syringe filter (DISMIC-25JP, Advancedtech, PTFE, 0.50 μm) was attached thereto. A polycarbonate resin substrate is fixed to a photoresist spinner (K-359S-1 manufactured by Kyowa Riken Co., Ltd.), 4 to 5 drops of an organosiloxane composition solution is dropped on the substrate, and the entire substrate is flow-coated. Was rotated at a rotation speed of 500 rpm for 2 seconds, and further rotated at a rotation speed of 1500 rpm for 50 seconds to spin-coat the solution onto the substrate and dried at room temperature.

(Vacuum ultraviolet light irradiation)
The surface of the spin-coated organosiloxane composition was irradiated with vacuum ultraviolet light using a vacuum ultraviolet light irradiation apparatus shown in FIG. As a vacuum ultraviolet light source, a xenon excimer lamp (UER20H-172VB, 50 mWcm ⁻² manufactured by USHIO INC.) That emits light of 172 nm was used. The irradiation distance (distance from the light source to the organosiloxane composition surface) was 1.5 cm. The irradiation intensity of vacuum ultraviolet light was separately measured at the same position as the surface of the organosiloxane composition using a vacuum ultraviolet light meter for measurement at 172 nm (“H8025-172 / C8026” manufactured by Hamamatsu Photonics Co., Ltd.). Value. The region for irradiation with vacuum ultraviolet light was mixed with lamp cooling nitrogen and air, and the oxygen partial pressure was adjusted by controlling the supply amount of each gas.

(Preparation of wear test samples)
The oxygen partial pressure at the time of vacuum ultraviolet light irradiation was 0.0 atm, 5.8 × 10 ⁻³ atm, 9.5 × 10 ⁻³ atm, 1.5 × 10 ⁻² atm, and 1.8 × 10 ⁻² atm, respectively. As described above, vacuum ultraviolet light was irradiated for 5 minutes to form a layer composed of an organosiloxane composition. The film thickness at this time was 1.15 μm.
In order to prepare a sample that can be subjected to a wear test, a laminate having a film thickness of 4.6 μm is prepared by repeating the application of the organosiloxane composition to vacuum ultraviolet light irradiation four times, and the wear test is performed on these. It was. The result is shown in FIG. In order to quantitatively show this result, the number of wear at each partial pressure of oxygen when the average transmittance was reduced to 75% was used as an index, and at the same time, the change in irradiation intensity obtained from the Lambert Bale equation was compared. The result is shown in FIG.
From FIG. 3 and FIG. 4, it became clear that the wear resistance is very good in the range where the oxygen partial pressure exists compared to the condition without oxygen (0.0 atm). In addition, in the apparatus system used in this example, the irradiation intensity of vacuum ultraviolet light was reduced due to an increase in oxygen partial pressure under the condition of oxygen partial pressure exceeding 1.5 × 10 ⁻² atm. It was estimated that the wear resistance was reduced.

In order to further clarify that the improvement in wear resistance depends on the partial pressure of oxygen, a detailed study was conducted on the condition of constant irradiation intensity. Specifically, the total amount of light irradiated was made the same by extending the irradiation time in accordance with the increase in oxygen partial pressure. FIG. 5 shows the results of using the number of wear at each oxygen partial pressure when the average transmittance is reduced to 75% as an index. From this result, when the total amount of light was the same (13 mW / cm ² × 5 minutes), an improvement in wear resistance due to an increase in oxygen partial pressure was observed. Note that the apparatus used in the examples does not describe the effect of the oxygen partial pressure of 0.02 atm or more because the irradiation light intensity is below the lower limit that can be controlled at the oxygen partial pressure of 0.02 atm or more. It is expected that a steady state is obtained on the extension line of the result of 5.

  Since the laminate of the present invention can be suitable for various uses that require surface hardness, abrasion resistance, scratch resistance, transparency and / or lightness, for example, window materials, headlights, etc. Various vehicle applications such as automobiles such as automobile cover materials, roofing materials, etc .; civil engineering and architectural applications such as window glass, outer wall materials, windshield glass, and road noise barriers; electrical and electronic parts applications such as display face plates and mobile phone components; eyeglasses It is expected that it can be used for a wide range of applications such as optical applications such as lenses.

1: Inert gas 2: Air 3: Curing organosiloxane composition 4: Light source 5: Sample stage 10: Vacuum ultraviolet light irradiation device

Claims (8)

  In the method for producing a laminate in which a plastic substrate and a layer made of an organosiloxane composition are laminated, the layer made of the organosiloxane composition is cured by irradiation with vacuum ultraviolet light in a state in which an oxygen partial pressure is adjusted. A method for producing a laminate, wherein the laminate is formed.   The method for producing a laminate according to claim 1, wherein the organosiloxane composition contains a hydrolyzable silicon compound derivative.   The method for producing a laminate according to claim 2, wherein the hydrolyzable silicon compound derivative is a hydrolyzate of alkoxysilane.   The said alkoxysilane is methyl triethoxysilane, The manufacturing method of the laminated body of Claim 3 characterized by the above-mentioned.   The said organosiloxane composition contains the derivative | guide_body of colloidal silica with an average particle diameter of 1 nm or more and 200 nm or less, The manufacturing method of the laminated body of any one of Claims 1-4 characterized by the above-mentioned. The oxygen partial pressure at the time of the vacuum ultraviolet light irradiation is 1.0 × 10 ⁻³ atm or more and 5.0 × 10 ⁻¹ atm or less, the lamination according to claim 1, Body manufacturing method.   The said plastic base material contains polycarbonate resin, The manufacturing method of the laminated body of any one of Claims 1-6 characterized by the above-mentioned.   The laminated body obtained by the manufacturing method of the laminated body of any one of Claims 1-7.

Images