JP5846434B2 - Resin laminate - Google Patents

Description

  The present invention relates to a resin laminate.

  In recent years, there has been a movement to apply a transparent resin molded body to a window glass, particularly an automobile window glass, for the purpose of reducing the weight. The molded body of the transparent resin is inferior in wear resistance and weather resistance as compared with the conventional glass molded body. In order to impart higher wear resistance and weather resistance to transparent resin moldings, it has been proposed to form a primer layer on the surface of the transparent resin molding and further to form a hard coat layer thereon. ing. For example, in Patent Document 1, a primer layer made of a thermosetting acrylic resin is formed on a polycarbonate molded body, and a siloxane obtained by thermosetting a component containing colloidal silica and trialkoxysilane hydrolysis condensate on the primer layer. A coated polycarbonate plate-like molded body in which a hard coat layer made of a system cured film is formed is disclosed. However, there is no molded article having a hard coat layer made of such a siloxane-based cured film yet has sufficient abrasion resistance to be required for a window glass, particularly an automobile window glass.

  In Patent Document 2, an actinic ray-cured layer and a hard coat layer containing at least 50% by mass or more of silicon oxide formed by a vacuum film forming process or a vacuum deposition method are laminated in this order on a polymer resin substrate. A polymer resin laminate is disclosed. By having silicon oxide in the hard coat layer, the abrasion resistance of the polymer resin molded article was higher than that of the molded article in which the hard coat layer made of a siloxane-based cured film was formed. However, the polymer resin molded body on which the hard coat layer containing silicon oxide is formed is not yet sufficiently durable as compared with glass.

Japanese Patent Laid-Open No. 2004-27110 JP 2001-322197 A

  The present invention has been made in view of the current state of the prior art described above, and its main purpose is to provide a resin laminate that is excellent in durability and that can particularly suppress the occurrence of cracks.

As a result of diligent research, the present inventors have determined that the hardness and elastic modulus on the surface side of the hard coat layer made of the SiO _x film are lower than the internal hardness and elastic modulus of the hard coat layer, thereby causing cracks in the resin laminate. It was found that the occurrence can be suppressed.

That is, the resin laminate of the present invention includes a transparent resin base material, a primer layer formed on the surface of the transparent resin base material and made of a resin primer containing an ultraviolet absorber, and SiO _x formed on the surface of the primer layer. A hard coat layer made of a film (1 ≦ x ≦ 2), and the SiO _x film has at least an outermost layer and an inner layer, and the hardness of the outermost layer is lower than the hardness of the inner layer and The elastic modulus of the outer layer is characterized by being lower than the elastic modulus of the inner layer.

Further, the SiO _x film further has an innermost layer on the surface on the primer layer side, the hardness of the innermost layer is preferably lower than the hardness of the inner layer, and the elastic modulus of the innermost layer is preferably lower than the elastic modulus of the inner layer. .

The SiO _x film is preferably formed by chemical vapor deposition (CVD).

The resin laminate of the present invention has a hard coat layer made of SiO _x film (1 ≦ x ≦ 2), and the SiO _x film has at least an outermost layer and an inner layer, and the hardness of the outermost layer is the inner layer. By making the elastic modulus of the outermost layer lower than that of the inner layer and lowering the elastic modulus of the inner layer, the occurrence of cracks can be suppressed and the durability is excellent.

It is a schematic diagram of the cross section of the resin laminated body of the prior art example after an endurance test. 3 is a schematic cross-sectional view of a resin laminate of Example 1. FIG.

  Below, the best form for implementing the resin laminated body of this invention is demonstrated using figures.

First, a conventional example will be described. A transparent resin substrate, a primer layer and a hard coat layer made of SiO _x film, conventional resin laminate comprising a temperature, humidity, by light, cracks STARTING FROM SiO _x film is produced. For example, an example is shown in FIG. FIG. 1 is a schematic cross-sectional view of a conventional resin laminate after an endurance test. In FIG. 1, the primer layer 2 is formed on the polycarbonate substrate 1 and the SiO _x film 3 is formed on the primer layer 2. In this example, the thickness of the primer layer 2 was about 10 μm, and the thickness of the SiO _x film 3 was about 3 μm. As shown in FIG. 1, cracks 4 occurred in the resin laminate after the durability test. The crack 4 extended to the polycarbonate substrate 1 starting from the SiO _x film 3. The SiO _x film generally contains C element and H element contained during its manufacture. Temperature endurance test, humidity, with light, C elements and H element contained in the SiO _x film is modified, the structure of the SiO _x film 3 is changed, SiO _x film 3 becomes brittle. Further, the polycarbonate substrate 1 and the primer layer 2 are expanded and contracted by the temperature, humidity, and light in the durability test. The SiO _x film 3, stress is applied by the expansion and contraction of the polycarbonate substrate 1 and the primer layer 2, a crack is generated in the SiO _x film 3 by starting from the position became brittle. Since the adhesion between the layers is high, the crack extends to the primer layer 2 and the polycarbonate substrate 1 as the base.

In order to suppress the occurrence of such cracks in the conventional SiO _x film, the resin laminate of the present invention has the following configuration. FIG. 2 shows a schematic diagram of a cross section of the resin laminate of Example 1 as an example. The resin laminate of the present invention includes a transparent resin substrate 10, a primer layer 20 including an ultraviolet absorber 50 formed on the surface of the transparent resin substrate 10, and a hard coat formed on the surface of the primer layer 20. The SiO _x film 30 (1 ≦ x ≦ 2) to be a layer is included, and the SiO _x film 30 includes at least an outermost layer 310 and an inner layer 320. The outermost layer 310 has a lower hardness than the inner layer 320, and the outermost layer 310 has a lower elastic modulus than the inner layer 320. Since the SiO _x film 30 has an outermost layer that is a starting point of cracks as a softer layer than the inside, the outermost layer 310 can flexibly follow the expansion and contraction of the transparent resin base material 10 and the primer layer 20, and the outermost layer. The occurrence of cracks in 310 can be suppressed. Further, since the SiO _x film 30 has the inner layer 320 having higher hardness and elastic modulus than the outermost layer 310, it has excellent wear resistance.

FIG. 2 shows a configuration in which the SiO _x film 30 further includes an innermost layer 330 on the surface on the primer layer 20 side. The innermost layer 330 has a lower hardness than the inner layer 320, and the innermost layer 330 has a lower elastic modulus than the inner layer 320. If the SiO _x film 30 has the innermost layer 330, the SiO _x film 30 has a flexible layer on the primer layer side, so that the adhesion between the primer layer 20 and the SiO _x film 30 is improved. In the case of the configuration of FIG. 2, the outermost layer 310 can suppress the occurrence of cracks, the inner layer 320 can impart high wear resistance to the resin laminate, and the innermost layer 330 can improve the adhesion with the primer layer.

Each configuration will be described in detail below.
(Resin laminate)
_{X of the} SiO _x film satisfies 1 ≦ x ≦ 2. More preferably, x is 1.2 ≦ x ≦ 2. For the purpose of obtaining higher transparency, x is preferably closer to 2. If _{x of the} SiO _x film is 1 ≦ x ≦ 2, the wear resistance and scratch resistance are good, and the crack resistance and adhesion with the primer layer are also excellent. It is preferable that x is close to 2 in terms of wear resistance and scratch resistance, and that x is smaller than 2 is preferable in terms of crack resistance and adhesion to the primer layer. The hardness of the SiO _x film closer x is 2 is higher, the higher the modulus of SiO _x film.

In addition to the Si element and the O element, the SiO _x film contains a C element and / or an H element contained during the production thereof.

In the present invention, the SiO _x film has at least an outermost layer and an inner layer, the hardness of the outermost layer is lower than the hardness of the inner layer, and the elastic modulus of the outermost layer is lower than the elastic modulus of the inner layer. Since the hardness and elastic modulus of the outermost layer that becomes the surface of the SiO _x film are low, the surface that is the starting point of the crack is flexible, and it is difficult to make the starting point of the crack, and as a result, the crack is not easily generated. Become. The hardness of the outermost layer is preferably higher than 1/2 of the hardness of the inner layer, and the elastic modulus of the outermost layer is preferably higher than 1/2 of the elastic modulus of the inner layer. If the hardness and elastic modulus of the outermost layer are lower than ½ of the hardness and elastic modulus of the inner layer, it is not preferable in terms of lowering the wear resistance and scratch resistance of the outermost layer, and the film of the outermost layer and the inner layer. Since the physical properties are different, it is not preferable in that the adhesion between the outermost layer and the inner layer is deteriorated.

  The hardness of the outermost layer may be constant within the layer, or may decrease continuously or stepwise from the inside toward the outside within the layer. Similarly, the hardness of the inner layer may be constant within the layer, or may decrease continuously or stepwise from the inside toward the outside within the layer. Further, the hardness of the outermost layer and the hardness of the inner layer may be continuously reduced.

  Further, the elastic modulus of the outermost layer may be constant within the layer, or may decrease continuously or stepwise from the inside toward the outside within the layer. Similarly, the elastic modulus of the inner layer may be constant within the layer, or may decrease continuously or stepwise from the inside toward the outside within the layer. Further, the elastic modulus of the outermost layer and the elastic modulus of the inner layer may be continuously lowered.

Furthermore, the SiO _x film preferably has an innermost layer on the surface on the primer layer side, the hardness of the innermost layer is lower than the hardness of the inner layer, and the elastic modulus of the innermost layer is preferably lower than the elastic modulus of the inner layer. . Since the SiO _x film has a flexible innermost layer on the primer layer side, adhesion with the primer layer is improved. For the same reason as described above, the hardness and elastic modulus of the innermost layer are preferably higher than ½ of the hardness and elastic modulus of the inner layer. Further, the hardness of the innermost layer may be constant within the layer, or may decrease continuously or stepwise from the inside toward the primer side within the layer. Similarly, the elastic modulus of the innermost layer may be constant within the layer, or may decrease continuously or stepwise from the inside toward the primer layer side within the layer. Further, the hardness of the inner layer and the hardness of the innermost layer may continuously decrease toward the primer layer side. Further, the elastic modulus of the inner layer and the elastic modulus of the innermost layer may continuously decrease toward the primer layer side.
Also, the outermost layer, inner layer, and innermost layer of the SiO _x film are continuously changed in hardness and elastic modulus so that the hardness and elastic modulus are generally high, the inner layer is high, and the outermost surface and primer layer side are low. It may be an inclined structure.

If the film thickness of the outermost layer, the inner layer, and the innermost layer is too thick compared to other layers, cracks are likely to occur. Therefore, the thickness of the inner layer is preferably 10 times or less than the thickness of the outermost layer. Further, if the inner layer is not thick to some extent, it is not preferable in terms of wear resistance. Therefore, the thickness of the inner layer is preferably 1 μm or more and 20 μm or less. The thickness of the outermost layer is preferably 0.1 μm or more and 2 μm or less. If the thickness of the outermost layer is within this range, cracks are unlikely to occur. The thickness of the innermost layer is preferably 0.1 μm or more and 10 μm or less. When the thickness of the innermost layer is within this range, the adhesion between the SiO _x film and the primer layer is good.

The SiO _x film can be formed by a coating method or a vacuum film forming method.

The coating method is a method of coating a coating composition made of a silicon-containing polymer, and the SiO _x film is formed by curing the coating composition.

Examples of the vacuum film forming method include a vacuum deposition method, a sputtering method, and a chemical vapor deposition method (CVD method). In particular, the SiO _x film is preferably formed by a chemical vapor deposition method (CVD method), particularly a plasma CVD method.

  In the plasma CVD method, an electric field is applied to the space in the vicinity of the substrate to generate a space (plasma space) where the gas in the plasma state exists, and the volatilized and sublimated organometallic compound is introduced into the plasma space and decomposed. A metal oxide thin film is formed by spraying on the substrate after the reaction has occurred. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the gas temperature is kept low, the electron temperature is very high. Therefore, the organometallic compound as the raw material of the inorganic film is decomposed even at a low temperature and can be formed even at a low temperature because it is in contact with this high-temperature electron or an excited state gas such as ions and radicals at a low temperature. Therefore, since the substrate is not heated to a high temperature, it is possible to sufficiently form a film on the resin substrate.

The SiO _x film obtained by the plasma CVD method can have various characteristics by selecting conditions such as a silicon compound as a raw material (also referred to as a raw material), oxygen as a decomposition gas, a decomposition temperature, and input power. In the plasma space, highly active charged particles and active radicals are present in high density, so that multistage chemical reactions are accelerated very rapidly in the plasma space, and the elements existing in the plasma space are thermodynamically Converts to a stable compound in a short time.

  The silicon compound may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  Examples of the silicon compound include silane, tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, and dimethyldiethoxy. Silane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane (HMDSO), bis ( Dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) Carbodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldi Silazane, tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyl Limethylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetra Examples include methylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, and M silicate 51.

  A discharge gas that is likely to be in a plasma state is mixed with a reactive gas composed of a source gas composed of a silicon compound and a decomposition gas composed of oxygen, and the gas is sent to a plasma discharge generator. As such a discharge gas, oxygen gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, oxygen, nitrogen, helium, and argon are preferably used.

The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas. In addition, the hardness and elastic modulus of the film can be changed by changing the relative amounts of silicon compound and oxygen supplied. When forming a SiO _x film, it is possible to increase the hardness and elastic modulus of the SiO _x film by more than the amount of oxygen in the amount of silicon compound. Also if slow deposition rate of the SiO _x film, it is possible to increase the hardness and elastic modulus of the SiO _x film.

  The transparent resin substrate is not particularly limited as long as it is a substrate made of a resin material having characteristics such as impact resistance and transparency. For example, if it is used as an organic glass for an automobile window glass, a transparent resin substrate such as polycarbonate, polymethyl methacrylate, or polystyrene is preferred. The transparent resin substrate is preferably a polycarbonate substrate.

The resin laminate of the present invention has a primer layer made of a resin primer. The primer layer improves the adhesion between the transparent resin substrate and the SiO _x film. Since the primer layer consists of resin primers, additional properties such as hardness, wear resistance, and light properties can be obtained by mixing resin primers with different properties and mixing additives such as fine particles of metals and oxides. Can be easily added.

  Although the resin primer which forms a primer layer will not be specifically limited if it is a general resin primer, As a preferable resin primer, a thermosetting resin primer or an ultraviolet curable resin primer is mentioned.

  Various thermosetting resin primers such as epoxy resin, urethane resin, polyester resin, melamine resin, phenol resin, polyamide, ketone resin, vinyl resin, thermosetting acrylic resin, acrylic resin modified with silane or siloxane, etc. An acrylic resin can be mentioned. Moreover, these can also be used individually or in combination of 2 or more types. Among these, an acrylic primer mainly containing various acrylic resins is particularly preferable.

  As an acrylic primer, specifically, a thermosetting and / or moisture curable (meth) acrylic resin which is a copolymer containing a reactive group-containing (meth) acrylic acid derivative as a monomer component, Examples thereof include thermoplastic (meth) acrylic resins made of reactive (meth) acrylic acid esters.

  Examples of reactive group-containing (meth) acrylic acid derivatives include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 1- [3- (meth) acryloxypropyl] pentamethoxydisilane, 1- [3- (meth) acryloxypropyl] -1-methyl-tetramethoxydisilane, 3- (meth) acryloxypropylsilane and tetramethoxysilane Alkoxysilyl group-containing (meth) acrylic acid derivatives such as co-hydrolyzed condensate with 1, co-hydrolyzed condensate of 3- (meth) acryloxypropylsilane and methyltrimethoxysilane; 2-hydroxyethyl (meth) acrylate , 3-hydroxypropyl (meth) acrylate, 4-hydro Cibutyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate (the number of ethylene glycol units is, for example, 2 to 20), polypropylene glycol mono (meth) acrylate (propylene The number of glycol units is, for example, mono (meth) acrylic acid esters of polyhydric alcohols such as 2 to 20); (meth) acrylic acids such as (meth) acrylic acid; 2-aminoethyl (meth) acrylate, (meth) ) Amino group-containing (meth) acrylic acid esters such as 2- (N-methylamino) ethyl acrylate; and epoxy group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate.

  Non-reactive (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acryl N-decyl acid, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, (meth ) Isobornyl acrylate, dicyclopentanyl (meth) acrylate, dicyclo (meth) acrylate (Meth) acrylic acid esters of monohydric alcohols such as tertenyloxyethyl and benzyl (meth) acrylate; (meth) acrylic acid monomers having a cyclic hindered amine structure; 2- (2′-hydroxy-5 ′) -(Meth) acryloxyphenyl) -2H-benzotriazole, 2- [2'-hydroxy-5 '-(2- (meth) acryloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy -3′-methyl-5 ′-(8- (meth) acryloxyoctyl) phenyl] -2H-benzotriazole, 2-hydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4 -(4- (meth) acryloxybutoxy) benzophenone, 2,2'-dihydroxy-4- (2- (meth) acryloxyate Xyl) benzophenone, 2,4-dihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2,2 ′, 4-trihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, Contains UV-absorbing groups such as 2-hydroxy-4- (3- (meth) acryloxy-2-hydroxypropoxy) benzophenone and 2-hydroxy-4- (3- (meth) acryloxy-1-hydroxypropoxy) benzophenone (meta ) Acrylic acid derivatives can be mentioned.

  As the ultraviolet curable resin primer, for example, one or more of (meth) acrylates having two or more functional groups in a molecule or a unit repeating structure can be used.

  Examples of such (meth) acrylates include dicyclopentanyl diacrylate, dicyclopentanyl dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, pentaerythritol. Tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, polyfunctional (meth) acrylate containing an isocyanur ring (number of functional groups: about 3 to 15), polyfunctional (meth) acrylate having an isocyanate bond (number of functional groups: 2 About 6. These are generally called urethane acrylates), so-called polyester acrylates (for example, “Aroni” manufactured by Toagosei Chemical) Box M8030, M8060, M8100, M8530, M8560, M9050 ", etc.) and the like are preferably exemplified.

  The primer layer contains an ultraviolet absorber. The primer layer containing the ultraviolet absorber can suppress the photodegradation of the transparent resin substrate. As a result, the weather resistance adhesion between the transparent resin substrate and the primer layer is improved.

  As the ultraviolet absorber, various commonly used inorganic and organic ultraviolet absorbers can be used, for example. Examples of the UV absorber include compound derivatives such as hydroxybenzophenone-based, benzotriazole-based, cyanoacrylate-based, and triazine-based main skeletons, and polymers such as vinyl polymers containing these UV absorbers in the side chains. Specifically, 2,4′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2,2′-dihydroxy-4,4′-diethoxybenzophenone, 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzofe 2,2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2- (2-hydroxy-5-t-methylphenyl) benzotriazole, 2- (2 -Hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyltriazine, 4- (2-acryloxyethoxy) -2-hydroxybenzophenone polymer 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-ben Polymers like triazole is exemplified. Among these, 2,2 ', 4,4'-tetrahydroxybenzophenone is preferably used from the viewpoint of volatility. Two or more of these organic ultraviolet absorbers may be used in combination.

  Moreover, you may use the fixed ultraviolet absorber fixed to the resin primer by the chemical bond as a ultraviolet absorber. Since the immobilized ultraviolet absorber has low sublimability, it is possible to suppress the disappearance of the ultraviolet absorber over time due to light or water. As a result, it is possible to reduce UV degradation on the surface of the transparent resin substrate and to maintain the adhesion between the transparent resin substrate and the primer layer.

The amount of the UV absorber fixed in the primer layer is preferably 1 to 25% by mass with respect to 100% by mass of the primer layer. If it is less than this, the ultraviolet-absorbing performance will not be sufficient, and the weather-resistant adhesiveness will fall. If it is more than this, the adhesion between the primer layer and the SiO _x film is lowered, and it becomes difficult to adhere from the beginning. A more preferable amount of the ultraviolet absorber is 3 to 15% by mass.

The thickness of the primer layer depends on the type of resin primer used as the primer and the type of ultraviolet absorber, but the thickness of the primer layer is preferably 5 μm or more. If the thickness of a primer layer is 5 micrometers or more, since the upper limit of the ultraviolet absorber which can be added to a primer layer increases, the photodegradation of a transparent resin-made base material can be reduced more effectively. As a result, the weather resistance adhesion between the transparent resin substrate and the primer layer is further improved. The thickness of the primer layer is more preferably 10 μm to 40 μm. If the thickness of the primer layer is within this range, good weather resistance can be imparted to the resin laminate while sufficiently bonding the transparent resin substrate and the SiO _x film.

  The primer layer may further contain other additives as required. Examples of other additives include curing agents or curing catalysts such as photopolymerization initiators, photopolymerization initiation assistants (sensitizers), leveling agents, light stabilizers (antioxidants), antifoaming agents, and thickeners. Is mentioned.

  The primer layer is formed on a transparent resin substrate. In order to form a primer layer on a transparent resin substrate, the primer is diluted with a solvent and, if necessary, a solution to which the ultraviolet absorber or the like is added may be applied to the surface of the transparent resin substrate. . Examples of the solvent include diacetone alcohol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, isobutyl alcohol, isopropyl alcohol, n-butyl alcohol, n-propyl alcohol, acetone, methyl ethyl ketone, Examples thereof include methyl isobutyl ketone, acetylacetone, ethyl acetate, butyl acetate, xylene, toluene and the like.

  As mentioned above, although embodiment of the resin laminated body of this invention was described, this invention is not limited to the said embodiment. The present invention can be implemented in various forms without departing from the gist of the present invention, with modifications and improvements that can be made by those skilled in the art.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  A polycarbonate plate having a thickness of 5 mm was prepared as a transparent resin substrate. Photocurable urethane acrylate (manufactured by Toagosei Co., Ltd., product number M313) was prepared as a primer resin. MAC-SQ (manufactured by Toagosei Co., Ltd.) was prepared as an inorganic additive. RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) was prepared as an ultraviolet absorber.

  Primer resin in which the primer resin, inorganic additive, ultraviolet absorber, other additives (radical polymerization initiator, light stabilizer, leveling agent), and solvent are blended in a ratio of 72: 15: 10: 3: 100 A mixture was prepared.

  Hexamethyldisiloxane (HMDSO) (manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared as a silicon compound as a raw material for the CVD film.

(Example 1)
After applying the above-mentioned primer resin mixture to the surface of the polycarbonate plate material and drying it with a hot air dryer at 100 ° C. for 10 minutes, the surface of the polycarbonate plate is immediately irradiated with ultraviolet rays (at a coating surface temperature of 90 ° C.). A 15 μm primer layer was formed thereon.

A SiO _x film as shown in FIG. 2 on the primer layer of the polycarbonate plate on which the primer layer is formed using a vacuum plasma CVD film forming apparatus capable of controlling the raw material gas flow rate, power, and pressure under the conditions shown in Table 1 below. 3 layers were formed.

First, a polycarbonate plate having a primer layer formed therein was set in a film forming chamber of a vacuum plasma CVD apparatus, and evacuation was performed to reach a vacuum level of 1 × 10 ⁻³ Pa.

Oxygen as a discharge gas and reaction gas and HMDSO were introduced in relative amounts of the flow rates (unit: sccm) shown in Table 1, and plasma was generated by an AC power supply with an output of 4 kW. Three layers of SiO _x films were deposited so as to obtain the resin laminate of Example 1. The film formation time was 5 minutes.

  The first layer in Table 1 corresponds to the innermost layer 330 in FIG. 1, the second layer in Table 1 corresponds to the inner layer 320 in FIG. 1, and the third layer in Table 1 corresponds to the outermost layer 310 in FIG.

(Comparative Example 1)
A resin laminate of Comparative Example 1 was obtained in the same manner as in Example 1 except that the third layer was not formed and the first layer and the second layer were each 1 and 5 μm.

(Evaluation)
The hardness and elastic modulus of the film of each layer of Example 1 were measured by the nanoindentation method. As the nano indenter, a Triboscope manufactured by HYSITRON Corporation attached to an atomic force microscope (SPM9500J2 manufactured by SHIMADZU) was used. The results are shown in Table 2.

  As can be seen from Table 2, the third layer which is the outermost layer of Example 1 has the smallest film hardness and film elastic modulus compared to the other two layers, and the second layer which is the inner layer is the other two layers. The film hardness and the film elastic modulus were the largest compared to.

  The taper abrasion test and the accelerated weather resistance test of the resin laminates of Example 1 and Comparative Example 1 were performed.

(Taber abrasion test)
Based on ASTM D-1044, a Taber type abrasion test was conducted. The abrasion resistance was evaluated by measuring a haze difference ΔH (%) before and after the Taber abrasion test using a Taber abrasion tester. Here, the wear wheel was CS-10F, the load was 500 g, and the rotation speed was 1000 times. The smaller ΔH (%), the better the wear resistance.

(Accelerated weathering test)
According to JIS K5400, an accelerated test for 5000 hours was performed with a carbon arc sunshine weather meter, and adhesion (weather resistance adhesion) and presence of cracks were evaluated every 500 hours. In addition, the adhesiveness determined that the film | membrane did not peel when the cellophane tape was affixed and peeled off to the cured film. Moreover, the crack was determined to be good if no crack was found in the cured film by visual observation.
The results are shown in Table 3.

  From the results of the accelerated weathering test shown in Table 3, it was found that the resin laminate of Example 1 did not crack even after the 5000 hour accelerated weathering test. From the results of the taper abrasion test in Table 3, the difference in haze (ΔH (%)) between the resin laminate of Example 1 and the resin laminate of Comparative Example 1 is slightly higher than that of Comparative Example 1. However, it turned out to be almost the same. From this, it was found that the resin laminate of Example 1 has both good wear resistance and durability.

1: polycarbonate substrate, 2: primer layer, 3: SiO _x film, 4: crack, 10: transparent resin base material, 20: primer layer, 30: SiO _x film, 50: UV absorber.

Claims (5)

A transparent resin substrate;
A primer layer formed on the surface of the transparent resin substrate and made of a resin primer containing an ultraviolet absorber;
A hard coat layer comprising a SiO _x film (1 ≦ x ≦ 2) formed on the surface of the primer layer;
Have
The SiO _x film has at least the outermost layer and the inner layer, the hardness of the outermost layer is lower than the hardness of said inner layer, and the elastic modulus of the outermost layer is rather low than the elastic modulus of the internal layer ,
The thickness of the said inner layer is 1 micrometer or more and 20 micrometers or less, and the thickness of the said outermost layer is 0.1 micrometer or more and 2 micrometers or less, The resin laminated body characterized by the above-mentioned . The SiO _x film further has an innermost layer on the surface on the primer layer side, the hardness of the innermost layer is lower than the hardness of the inner layer, and the elastic modulus of the innermost layer is higher than the elastic modulus of the inner layer. The resin laminate according to claim 1, which is low. The resin laminate according to claim 2, wherein the innermost layer has a thickness of 0.1 μm to 10 μm.   The hardness and elastic modulus of the outermost layer are continuously lowered from the inside of the outermost layer toward the outside, and the hardness and elastic modulus of the innermost layer are continuously directed toward the primer layer in the innermost layer. The resin laminate according to claim 2 or 3, wherein the resin laminate is low. The resin laminate according to any one of claims 1 to 4, wherein the SiO _x film is formed by a chemical vapor deposition method (CVD method).

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