WO2012046784A1 - Substrat en résine auquel est fixé un film de revêtement dur et son procédé de production - Google Patents

Substrat en résine auquel est fixé un film de revêtement dur et son procédé de production Download PDF

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WO2012046784A1
WO2012046784A1 PCT/JP2011/073013 JP2011073013W WO2012046784A1 WO 2012046784 A1 WO2012046784 A1 WO 2012046784A1 JP 2011073013 W JP2011073013 W JP 2011073013W WO 2012046784 A1 WO2012046784 A1 WO 2012046784A1
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group
hard coat
resin substrate
organopolysiloxane
acrylic polymer
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PCT/JP2011/073013
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English (en)
Japanese (ja)
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澁谷　崇
今日子 山本
海田　由里子
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旭硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present invention relates to a resin substrate with a hard coat film and a method for producing the same.
  • a film that is, a hard coat layer on the surface of the transparent resin plate using various hard coat agents, particularly silicone hard coat agents. Proposed. At that time, it has also been proposed to provide a primer layer on the transparent resin plate in order to improve the adhesion between the hard coat layer and the transparent resin plate.
  • the adhesion and UV resistance are improved by using the primer layer compared to the treatment of only one hard coat layer.
  • problems in weather resistance such as generation of cracks after long-term use and deterioration of adhesion.
  • the weather resistance is that yellowing, cracking of the coating film, and peeling do not occur after long-term outdoor use, but in order to obtain a test result, a long time of several years to more than 10 years is required. Therefore, the weather resistance is generally evaluated by an accelerated weather resistance test in which ultraviolet rays, temperature and humidity environments are artificially set.
  • Patent Document 1 discloses a primer made of a copolymerized polymer of 3-methacryloxypropyltrimethoxysilane and a reactive ultraviolet absorber.
  • a resin substrate with a hard coat layer in which a layer is formed has been proposed.
  • Patent Document 2 proposes a resin substrate with a hard coat layer in which a primer layer is formed from a copolymerized polymer of methyl methacrylate, 3-methacryloxypropyltrimethoxysilane and a reactive ultraviolet absorber. .
  • Patent Document 3 discloses a primer layer forming composition
  • Japanese Unexamined Patent Publication No. 2001-47574 Japanese Unexamined Patent Publication No. 4-120181 Japanese Unexamined Patent Publication No. 2008-274177
  • the present invention was made in order to solve the above-described problems of the prior art, and in a resin substrate with a hard coat film in which a hard coat layer is provided on a resin substrate via a primer layer, the scratch resistance is improved.
  • Hard coat with excellent weather resistance such as adhesion after accelerated weathering test (hereinafter also referred to as “weather resistance”) and crack resistance after weathering test (hereinafter also referred to as “weather cracking”) It aims at providing the resin substrate with a film, and its manufacturing method.
  • the resin substrate with a hard coat film of the present invention has a primer layer containing an acrylic polymer as a main component on at least one surface of the resin substrate, and a hydrolyzable silyl group and / or SiOH group in the side chain.
  • An adhesive layer containing, as a main component, a silyl group-containing acrylic polymer that does not contain a polymer unit having an aromatic hydrocarbon group in the side chain, and a hard coat layer containing a cured product of organopolysiloxane as a main component In order from the resin substrate side.
  • the method for producing a resin substrate with a hard coat film according to the present invention is a method for producing the resin substrate with a hard coat film according to the present invention, wherein the acrylic polymer is formed on at least one surface of the resin substrate.
  • the composition for forming an adhesive layer containing as a main component an silyl group-containing acrylic polymer that does not contain a polymer unit having an aromatic hydrocarbon group in the side chain and drying to form the adhesive layer;
  • a hard coat layer-forming composition containing the organopolysiloxane as a main component is applied and cured to form the hard coat layer.
  • the “hard coat film” refers to a multi-layered film including a hard coat layer formed on a resin substrate. That is, in the present invention, the entire film having the primer layer, the adhesive layer, and the hard coat layer is referred to as “hard coat film”.
  • the “hydrolyzable silyl group” refers to a silyl group in which a hydrolyzable group is directly bonded to a silicon atom.
  • the “hydrolyzable group” refers to a group that becomes a hydroxyl group (—OH group) by hydrolysis. Therefore, the “hydrolyzable silyl group and / or SiOH group” means a silyl group in which a hydrolyzable group is bonded to a silicon atom, including those partially hydrolyzed to a hydroxyl group (—OH group). means. Specific examples of the hydrolyzable group will be described in detail later.
  • the “main component” means that the primer layer, the adhesive layer and the hard coat layer contain 50 to 100% by mass of the main component material with respect to the entire material constituting each layer. To do.
  • the resin substrate with a hard coat film of the present invention is excellent in scratch resistance and weather resistance such as weather adhesion and weather cracking. Moreover, according to the manufacturing method of this invention, the resin substrate with a hard coat film which is excellent in abrasion resistance and also in weather resistance can be obtained.
  • FIG. 1 shows an embodiment of a resin substrate with a hard coat film of the present invention.
  • the resin substrate 1 with a hard coat film has a primer layer 3 containing an acrylic polymer as a main component (hereinafter also referred to as “acrylic primer layer”) and side chains on one surface of a resin substrate 2.
  • acrylic primer layer an acrylic polymer as a main component
  • a hard coat layer 5 containing a cured product of siloxane as a main component (hereinafter sometimes referred to as “silicone-based hard coat layer”) has a configuration in which the layers are laminated in this order.
  • the resin substrate 1 with a hard coat film of the present invention has a hydrolyzable silyl group and / or SiOH group in the side chain between the acrylic primer layer 3 and the silicone hard coat layer 5 and is aromatic. Since the adhesive layer 4 containing as a main component a silyl group-containing acrylic polymer not containing a polymerization unit having a hydrocarbon group in the side chain is provided, the hard coat film has good scratch resistance and weather resistance adhesion. And weather resistance such as weather resistance crack resistance. That is, in the silyl group-containing acrylic polymer constituting the adhesive layer 4, the hydrolyzable silyl group and / or SiOH group contained in this polymer is the hydrolyzable silyl of the organopolysiloxane constituting the hard coat layer 5.
  • a siloxane bond (—O—Si—O—) is formed by reacting with a group and / or SiOH group, and therefore, adhesion between the adhesive layer 4 and the hard coat layer 5, particularly weather resistance adhesion Will improve. And since the adhesive layer 4 excellent in adhesiveness with the hard coat layer 5 is provided between the acrylic primer layer 3 and the silicone hard coat layer 5 in this way, weather resistance adhesion and weather crack resistance. Thus, a hard coat film having excellent weather resistance can be obtained.
  • the resin that is the material of the resin substrate used in the present invention includes polycarbonate resin, polystyrene resin, aromatic polyester resin, acrylic resin, polyester resin, polyarylate resin, and the weight of halogenated bisphenol A and ethylene glycol.
  • examples include condensates, acrylic urethane resins, and halogenated aryl group-containing acrylic resins.
  • the resin substrate may contain two or more types of thermoplastic resins as described above, or may be a laminated substrate in which two or more layers are laminated using these resins.
  • the shape of the resin substrate is not particularly limited, and may be a flat plate or curved.
  • the color tone of the resin substrate is preferably colorless and transparent or colored and transparent. What is necessary is just to select the thickness of a resin substrate suitably by a use. In the case of window materials, the thickness of the resin substrate is preferably 1 mm to 30 mm, more preferably 2 mm to 20 mm.
  • the resin substrate with a hard coat film of the present invention has a primer layer containing an acrylic polymer as a main component on at least one surface of the resin substrate.
  • a primer layer is provided in order to improve the adhesiveness of a resin substrate and a hard-coat layer with the contact bonding layer mentioned later. Since the primer layer of the resin substrate with a hard coat film of the present invention is in direct contact with the resin substrate, adhesion with the resin substrate is ensured. Moreover, the adhesiveness between a primer layer and a hard-coat layer is ensured through the contact bonding layer mentioned later.
  • acrylic polymer for the primer layer As the acrylic polymer that is the main component of the primer layer (hereinafter sometimes referred to as “acrylic polymer for the primer layer”), it is usually used as a primer layer for adhering the resin substrate and the silicone hard coat layer.
  • the acrylic polymer used is not particularly limited.
  • a homopolymer or copolymer (copolymer) having a monomer having an acrylic group or a methacryl group as a main monomer is used. More preferably, a monomer having a methacryl group is used.
  • the monomer having an acrylic group include acrylic acid esters. A methacrylic acid ester is mentioned as a monomer which has a methacryl group.
  • a methacrylic acid alkyl ester having an alkyl group having 6 or less carbon atoms is preferable. That is, as the acrylic polymer for the primer layer, at least one selected from the group consisting of alkyl methacrylates having an alkyl group having 6 or less carbon atoms is used as a “main monomer” (specifically, the entire raw material monomer). A homopolymer of 90 to 100 mol%, the same shall apply hereinafter) and copolymers of these monomers are preferred. Examples of the homopolymer include polymethyl methacrylate.
  • a copolymer of a main monomer selected from the group consisting of alkyl methacrylates having an alkyl group having 6 or less carbon atoms and at least one of other acrylic esters and methacrylic esters is also preferable.
  • the other monomers include acrylic acid esters and methacrylic acid esters having an alkyl group having 7 or more carbon atoms or a cycloalkyl group having 12 or less carbon atoms.
  • the copolymer obtained by copolymerizing the acrylic acid ester and methacrylic acid ester which have the alkyl group containing a functional group like a hydroxyl group, or (meth) acrylic acid with these monomers can also be used.
  • cycloalkyl group examples include a cyclohexyl group, a 4-methylcyclohexyl group, a 4-t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyloxyethyl group.
  • the acid value of the acrylic polymer for the primer layer is preferably 1 mgKOH / g or less. When the acid value exceeds 1 mgKOH / g, cracks and the like are generated in the resulting film, which is not preferable in appearance.
  • the acid value of the acrylic polymer is more preferably 0.8 mgKOH / g or less, and particularly preferably 0 mgKOH / g.
  • the acid value refers to the number of milligrams of potassium hydroxide required to neutralize resin acid or the like in 1 g of a sample, and is a value that can be measured according to the measurement method of JIS K 0070.
  • the glass transition point of the acrylic polymer is preferably 60 ° C. to 150 ° C. If the glass transition point is less than 60 ° C., rough skin or the like is likely to occur in the resulting coating, and if it exceeds 150 ° C., the resulting coating is not sufficiently smooth, and both are not preferred in appearance.
  • the glass transition point of the acrylic polymer is more preferably 70 ° C. to 120 ° C., particularly preferably 90 ° C. to 110 ° C.
  • these acrylic polymers for primer layers preferably have a weight average molecular weight (Mw) of 20,000 or more, more preferably 50,000 or more, and a weight average molecular weight (Mw) of 1,300,000. Or less, more preferably 1,000,000 or less.
  • Mw weight average molecular weight
  • An acrylic polymer having a weight average molecular weight (Mw) in this range is preferable because it exhibits sufficient adhesion and strength performance as a primer layer.
  • a weight average molecular weight (Mw) means the value which measured polystyrene as a standard substance by the gel permeation chromatography method.
  • Such an acrylic polymer for the primer layer may be other than (meth) acrylic acid alkyl ester of less than 10 mol% based on the total amount of raw material monomer, if necessary, using the above various (meth) acrylic acid alkyl esters as raw material monomers
  • a method for polymerizing alkyl (meth) acrylates with monomers, molecular weight regulators, polymerization initiators, suspension stabilizers, emulsifiers, etc. such as solution polymerization, bulk polymerization, suspension polymerization, emulsion weight It can be produced by a polymerization method such as a legal method.
  • acrylic polymer is also commercially available.
  • these commercially available products such as Dianal LR269 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), weight average molecular weight : 100,000), LR248 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), weight average molecular weight: 155,000) and the like, and are commercially available as a solution previously dissolved in an appropriate solvent. You can use what you have.
  • Dianal BR80 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), weight average molecular weight: 90,000), Dianal BR88 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA)) , Weight average molecular weight: 430,000), M-4003 (trade name, manufactured by Negami Kogyo Co., Ltd., polymethyl methacrylate (PMMA), weight average molecular weight: 700,000-1,300,000), etc.
  • the polymer can be used by dissolving in a suitable solvent. Furthermore, it is also possible to use a mixture of two or more of these acrylic polymers.
  • the primer layer preferably contains an ultraviolet absorber.
  • an ultraviolet absorber it is preferable to use an ultraviolet absorber having an average absorption coefficient of 3.5 g / (mg ⁇ cm) to 100 g / (mg ⁇ cm) for light in the wavelength region of 350 nm to 380 nm. It is more preferably 0 g / (mg ⁇ cm) to 50 g / (mg ⁇ cm).
  • the average value of the extinction coefficient in the wavelength region of 350 to 380 nm refers to the average value of the extinction coefficient obtained every 1 nm in the wavelength region.
  • the extinction coefficient ⁇ is a value obtained from the following relational expression, Equation 1.
  • the absorption coefficient absorbs the ultraviolet rays in the range of 3.5 g / (mg ⁇ cm) to 100 g / (mg ⁇ cm) on average.
  • the primer layer contains a compound that can be used as an ultraviolet absorber. If the average value of the extinction coefficient at 350 to 380 nm is smaller than 3.5 g / (mg ⁇ cm), the obtained coating film may not be able to impart sufficient weather resistance to the resin substrate. Further, if it exceeds 100 g / (mg ⁇ cm), coloring is likely to occur because there is also absorption in the visible light region.
  • the ultraviolet absorber contained in the primer layer can be used without particular limitation as long as it has the above-mentioned light absorption characteristics. Specifically, a benzophenone ultraviolet absorber having the above light absorption characteristics, Triazole ultraviolet absorbers, benzimidazole ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, salicylate ultraviolet absorbers, benzylidene malonate ultraviolet absorbers, triazine ultraviolet absorbers, and the like can be used. These may use 1 type and may use 2 or more types together.
  • the content of the ultraviolet absorber in the primer layer is preferably 1 to 50 parts by mass, particularly preferably 1 to 30 parts by mass with respect to 100 parts by mass of a resin component such as an acrylic polymer.
  • the ultraviolet absorber contained in the primer layer is preferably at least one selected from the group consisting of benzophenones, triazines, and benzotriazoles.
  • the primer layer of the present invention contains an ultraviolet absorber, the acid value of the acrylic polymer contained in the primer layer is 1 mg KOH / g or less, the glass transition point is 60 ° C. to 150 ° C., and the weight average The molecular weight is 20,000 to 1,000,000, and the absorption coefficient for light in the wavelength region of 350 nm to 380 nm of the UV absorber is an average value of 3.5 g / (mg ⁇ cm) to 100 g / (mg ⁇ cm ) Is preferred.
  • the primer layer may further contain a light stabilizer and the like.
  • the light stabilizer include hindered amines; nickel complexes such as nickel bis (octylphenyl) sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate. These may use 1 type and may use 2 or more types together.
  • the content of the light stabilizer in the primer layer is preferably from 0.01 to 50 parts by weight, particularly preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of a resin component such as an acrylic polymer.
  • the method for forming the primer layer on at least one surface of the resin substrate is not particularly limited, but preferably, the acrylic polymer for the primer layer, the ultraviolet absorber, And a method for applying a primer layer-forming composition containing a solvent on a resin substrate and drying the composition.
  • the primer layer forming composition usually contains a solvent.
  • the solvent is not particularly limited as long as it can dissolve the acrylic polymer for primer stably.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane; esters such as ethyl acetate, butyl acetate and methoxyethyl acetate Methanol; ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methoxyethanol, diacetone alcohol, 2-butoxyethanol, 1-methoxy-2- Examples include alcohols such as propanol; hydrocarbons such as n-hexane, n-heptane, isoctane, benzene, toluene, xy
  • the amount of the solvent is preferably 50 to 10,000 parts by mass, particularly preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the resin component such as the acrylic polymer for the primer layer.
  • the content of the nonvolatile component (solid content) in the primer layer forming composition is preferably 0.5 to 75% by mass, particularly 1 to 60% by mass, based on the total amount of the composition. preferable.
  • the primer layer forming composition may further contain additives such as a leveling agent, an antifoaming agent and a viscosity modifier.
  • the method for applying the primer layer forming composition onto the resin substrate is not particularly limited, and examples thereof include a spray coating method, a dip coating method, a flow coating method, a die coating method, and a spin coating method.
  • the heating conditions for drying are not particularly limited, but are preferably 50 to 140 ° C. and 5 minutes to 3 hours.
  • the film thickness of the primer layer before forming the adhesive layer and the hard coat layer on the primer layer is such that the resin substrate with a hard coat film finally obtained satisfies the requirements required as a primer layer.
  • the thickness is appropriately adjusted in consideration of the thickness of the adhesive layer and the hard coat layer formed on the primer layer.
  • the film thickness of the primer layer is too thin, the weather cracking property, weather adhesion, and colorability after the weather test of the resin substrate with a hard coat film are lowered.
  • the film thickness of the primer layer in the resin substrate with a hard coat film finally obtained can be reduced compared to the film thickness before the formation of these layers due to the formation of the adhesive layer and the hard coat layer on the primer layer. Therefore, the thickness of the primer layer before forming the adhesive layer and the hard coat layer is necessary and sufficient to sufficiently adhere and bond the resin substrate and the hard coat layer through the adhesive layer. It is preferable that
  • the thickness of the primer layer before the adhesive layer and the hard coat layer are formed is preferably 0.1 ⁇ m to 10 ⁇ m, and particularly preferably 1 ⁇ m to 7 ⁇ m.
  • the resin substrate with a hard coat film of the present invention has an adhesive layer on a primer layer containing an acrylic polymer as a main component.
  • the adhesive layer is a layer provided to improve the adhesion and adhesion between the primer layer formed on the resin substrate and the hard coat layer described later, and has a hydrolyzable silyl group and / or a side chain.
  • a silyl group-containing acrylic polymer having a SiOH group is used as a main component.
  • the silyl group-containing acrylic polymer constituting the adhesive layer is an acrylic that contains a hydrolyzable silyl group and / or SiOH group in the side chain and does not contain a polymer unit having an aromatic hydrocarbon group in the side chain.
  • the side chain hydrolyzable silyl group and / or SiOH group should be interpreted as including a siloxane bond.
  • the silyl group containing acrylic polymer which comprises an contact bonding layer is demonstrated.
  • the hydrolyzable silyl group and / or SiOH group is preferably bonded to the hydrocarbon group constituting the side chain of the acrylic polymer via a C—Si bond.
  • the silyl group-containing acrylic polymer contains a polymer unit having one hydrolyzable silyl group and / or SiOH group in the side chain (hereinafter sometimes referred to as “silyl group-containing polymer unit”).
  • the number of hydrolyzable silyl groups and / or SiOH groups contained in each silyl group-containing polymer unit is usually one, but may be two or more.
  • a polymerization unit means the repeating unit which comprises a polymer (polymer).
  • the silyl group-containing acrylic polymer can have a hydroxyalkyl group having a hydroxyl group bonded to a carbon atom (hereinafter, also referred to as “C—OH” group) in the side chain. That is, in addition to the silyl group-containing polymer unit, the polymer unit may further have a polymer unit in which a hydroxyalkyl group is bonded to a side chain.
  • C—OH carbon atom
  • this silyl group-containing acrylic polymer does not contain a polymer unit having an aromatic hydrocarbon group such as an ultraviolet absorbing group. That is, it does not have a structure in which a monomer having an aromatic hydrocarbon group such as an ultraviolet absorbing group is copolymerized.
  • the silyl group-containing acrylic polymer has a structure in which a monomer having an aromatic hydrocarbon group such as an organic ultraviolet absorbing group is copolymerized, the reactivity with the organopolysiloxane constituting the hard coat layer is not good. It is sufficient, and improvement in adhesion, particularly weather resistance adhesion, cannot be expected. Further, the familiarity with the primer layer becomes insufficient, and as described later, the scratch resistance of the hard coat film cannot be sufficiently obtained.
  • silyl group-containing acrylic polymers a polymer having no hydroxyalkyl group (C—OH group) (hereinafter sometimes referred to as “silyl group-containing acrylic polymer (1)”) will be described.
  • the silyl group-containing acrylic polymer (1) comprises (A) an acrylic monomer having a hydrolyzable silyl group and / or SiOH group and containing no polymerized unit having an aromatic hydrocarbon group in the side chain (hereinafter, And (B) a polymer unit based on methyl methacrylate (MMA), (A) a silyl group-containing acrylic monomer, B) It can be obtained by copolymerizing a monomer component comprising MMA.
  • MMA methyl methacrylate
  • the silyl group-containing acrylic monomer (A) has a hydrolyzable silyl group and / or SiOH group bonded through one C—Si bond in one molecule, and one acrylic group.
  • any monomer having a methacryl group can be used without any particular limitation.
  • a methacrylic acid ester having one hydrolyzable silyl group and / or SiOH group is preferable.
  • the hydrolyzable silyl group is a group in which the hydrolyzable group is directly bonded to the silicon atom, and the hydrogen atom of the silyl group (—SiH 3 ) is substituted with the hydrolyzable group.
  • the hydrolyzable group is a group that becomes a hydroxyl group (OH group bonded to a silicon atom) by hydrolysis, and specifically includes a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
  • Alkoxy groups such as a methoxy group and an ethoxy group are preferred because of easy controllability of hydrolyzability and availability.
  • substituent other than the hydrolyzable group examples include an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group, and a phenyl group. From the viewpoint of availability, a methyl group is preferably used.
  • acrylic monomers to which such hydrolyzable silyl groups are bonded include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, and 3-methacryloxy.
  • acrylic monomers to which such hydrolyzable silyl groups are bonded include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, and 3-methacryloxy.
  • 3-methacryloxypropyltrimethoxysilane or 3-methacryloxypropylmethyldimethoxysilane is particularly preferable from the viewpoints of availability, handling, crosslink density, and reactivity.
  • the silyl group-containing acrylic polymer (1) is obtained by copolymerizing such a monomer component comprising (A) a silyl group-containing acrylic monomer and (B) methyl methacrylate (MMA). If necessary, (C) a copolymer obtained by copolymerizing another copolymerizable acrylic monomer may be used.
  • copolymerizable acrylic monomers (C) other than (A) and (B) include acrylic acid esters and methacrylic acid esters having an alkyl group having 2 to 18 carbon atoms, and cycloalkyl groups having 12 or less carbon atoms.
  • Acrylic acid ester or methacrylic acid ester, or an acrylic acid ester or methacrylic acid ester having an epoxy group, specifically, glycidyl methacrylate can be used.
  • the other copolymerizable acrylic monomer may be one type or two or more types. Among these, acrylic acid esters or methacrylic acid esters having a linear alkyl group having 2 to 16 carbon atoms are preferred.
  • ethyl methacrylate EMA
  • BMA n-butyl methacrylate
  • DMA decyl methacrylate
  • LMA Lauryl methacrylate
  • CMA cetyl methacrylate
  • Tg glass transition temperature
  • the content ratio of the polymerized units based on (B) methyl methacrylate (MMA) is 50% of the total polymer units constituting the silyl group-containing acrylic polymer (1). It is preferable to set it to -98 mol%. Further, the content ratio of the polymer units based on (A) the silyl group-containing acrylic monomer is preferably 0.5 to 50 mol% of the entire polymer units constituting the silyl group-containing acrylic polymer (1).
  • the copolymer composition in the silyl group-containing acrylic polymer (1) is that (B) the polymerization unit based on methyl methacrylate (MMA) is 50 to 98 mol%, and (A) the silyl group-containing acrylic monomer It is preferable that the polymerized units based on 0.5 to 50 mol%.
  • Particularly preferred copolymer composition is (B) 60 to 95 mol% of polymerized units based on methyl methacrylate (MMA) and (A) 5 to 40 mol% of polymerized units based on silyl group-containing acrylic monomer. is there.
  • the hydrolyzable silyl group and / or SiOH group contained in the polymerized unit constitutes a hard coat layer described later. Adhesiveness to the hard coat layer due to the formation of an adhesive layer without reaction with the terminal group of the organopolysiloxane (for example, Si—OX group, where —OX represents a hydroxyl group or an alkoxy group). The improvement effect cannot be obtained sufficiently.
  • the silyl group-containing acrylic polymer (1) is composed of (A) a silyl group-containing acrylic monomer, (B) methyl methacrylate (MMA), and, if necessary, (C) another acrylic monomer that can be copolymerized.
  • A a silyl group-containing acrylic monomer
  • B methyl methacrylate
  • C another acrylic monomer that can be copolymerized.
  • radical polymerization selected from the group consisting of peroxides such as dicumyl peroxide and benzoyl peroxide, or azo compounds such as 2,2′-azobis (isobutyronitrile) It can be easily obtained by adding an initiator and reacting under heating (40 to 150 ° C., particularly 50 to 120 ° C. for 1 to 10 hours, particularly 3 to 8 hours).
  • silyl group-containing acrylic polymer (1) for example, a copolymer of (A) 3-methacryloxypropyltrimethoxysilane, which is a silyl group-containing acrylic monomer, and (B) methyl methacrylate (MMA)
  • the silyl group-containing acrylic polymer is represented by the following composition formula.
  • X and Y represent the molar ratio of (B) polymerized units based on methyl methacrylate (MMA) and (A) polymerized units based on 3-methacryloxypropyltrimethoxysilane, respectively.
  • MMA methyl methacrylate
  • A polymerized units based on 3-methacryloxypropyltrimethoxysilane
  • X + Y 100
  • X: Y ratio is preferably 50:50 to 98: 2.
  • silyl group-containing acrylic polymer (2) a silyl group-containing acrylic polymer having a hydroxyalkyl group (C—OH group) (hereinafter referred to as silyl group-containing acrylic polymer (2)) will be described.
  • the silyl group-containing acrylic polymer (2) includes a polymer unit in which a hydrolyzable silyl group and / or SiOH group is bonded to the side chain via a C—Si bond (silyl group-containing polymer unit), and a hydroxy group in the side chain.
  • Each has a polymer unit having an alkyl group (C—OH group) (hereinafter sometimes referred to as “C—OH group-containing polymer unit”) and a polymer unit based on (B) methyl methacrylate (MMA).
  • the silyl group-containing polymer unit is obtained, for example, by polymerization of (A) an acrylic monomer having a hydrolyzable silyl group and / or SiOH group bonded via a C—Si bond (silyl group-containing acrylic monomer). be able to. Further, the C—OH group-containing polymer unit is obtained by polymerization of (D) an acrylic monomer having a hydroxyalkyl group (C—OH group) (hereinafter sometimes referred to as “C—OH group-containing acrylic monomer”). Obtainable. Furthermore, a silyl group-containing polymer unit can also be obtained by modifying a part of the C—OH group-containing polymer unit thus obtained by the method described later.
  • silyl group-containing acrylic monomer and (B) methyl methacrylate (MMA) are as described for the silyl group-containing acrylic polymer (1).
  • Examples of (D) C—OH group-containing acrylic monomers include 2-hydroxyethyl (meth) acrylate (also referred to as 2-hydroxyethyl (meth) acrylate), 2-hydroxypropyl (meth) acrylate, hydroxydiethylene glycol ( And (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like.
  • the silyl group-containing acrylic polymer (2) comprises (C) a copolymer other than (A) a silyl group-containing acrylic monomer, (B) methyl methacrylate (MMA) and (D) a C—OH group-containing acrylic monomer. It can have polymerized units based on polymerizable acrylic monomers.
  • C As other copolymerizable acrylic monomers, those described in the silyl group-containing acrylic polymer (1) can be used.
  • the content ratio of the polymer units based on (B) methyl methacrylate (MMA) is 50% of the total polymer units constituting the silyl group-containing acrylic polymer (2). It is preferable to set it to -98 mol%.
  • the content ratio of the silyl group-containing polymer units is preferably 0.5 to 50 mol% of the entire polymer units constituting the silyl group-containing acrylic polymer (2).
  • the silyl group-containing polymer unit When the silyl group-containing polymer unit is less than 0.5 mol%, the hydrolyzable silyl group and / or SiOH group of the polymer unit and the end group (for example, Si) of the organopolysiloxane constituting the hard coat layer described later are included.
  • —OX group (wherein —OX represents a hydroxyl group or an alkoxy group) is not sufficiently formed, and the effect of improving the adhesion with the hard coat layer due to the provision of the adhesive layer cannot be sufficiently obtained. .
  • the silyl group-containing polymer unit exceeds 50 mol%, the polymer unit based on (B) methyl methacrylate (MMA) is inevitably less than 50 mol%. Decreases. Moreover, since unreacted hydrolyzable groups are likely to remain, post-crosslinking with time may occur, and cracks may easily occur.
  • the content ratio of the C—OH group-containing polymer units is 0.5% of the total polymer units constituting the silyl group-containing acrylic polymer (2). It is preferable that the content be ⁇ 30 mol%. Furthermore, when the silyl group-containing acrylic polymer (2) contains a polymer unit based on the (C) other copolymerizable acrylic monomer, the content ratio of the polymer unit is silyl group-containing acrylic polymer ( It is preferably 0 to 45 mol% of the entire polymerized units constituting 2).
  • the particularly preferred copolymer composition of the silyl group-containing acrylic polymer (2) is (B) 50 to 95 mol% of polymer units based on methyl methacrylate (MMA) and 0.5 to 20 mol% of silyl group-containing polymer units.
  • the C—OH group-containing polymer units are 0.5 to 20 mol%, and the polymer units based on (C) other copolymerizable acrylic monomers are 0 to 40 mol%.
  • This silyl group-containing acrylic polymer (2) comprises, as shown in the following composition formula, (A) a polymer unit based on 3-methacryloxypropyltrimethoxysilane, which is a silyl group-containing acrylic monomer, and (B) methacrylic monomer.
  • MMA methyl acid
  • HEMA 2-hydroxyethyl methacrylate
  • C other copolymerizable acrylic monomers
  • LMA lauryl methacrylate
  • BMA n-butyl methacrylate
  • p, q, r, s, and t are respectively a polymer unit based on methyl methacrylate (MMA), a polymer unit based on lauryl methacrylate (LMA), and a polymer unit based on n-butyl methacrylate (BMA).
  • MMA methyl methacrylate
  • LMA lauryl methacrylate
  • BMA n-butyl methacrylate
  • Represents a molar ratio of polymerized units based on 3-methacryloxypropyltrimethoxysilane and polymerized units based on 2-hydroxyethyl methacrylate (HEMA), and p + q + r + s + t 100 holds.
  • the molar ratio p of polymerized units based on (B) methyl methacrylate (MMA) is preferably 50 to 95 as described above.
  • the molar ratio s of polymerized units based on (A) silyl group-containing acrylic monomer 3-methacryloxypropyltrimethoxysilane is preferably 0.5 to 20, and (D) C—OH group-containing
  • the molar ratio t of polymerized units based on acrylic monomer 2-hydroxyethyl methacrylate (HEMA) is preferably 0.5-20.
  • the molar ratios q and r of polymerized units based on (C) other copolymerizable acrylic monomers lauryl methacrylate (LMA) and n-butyl methacrylate (BMA) are 0 to 20 and 0 to 30, respectively. And the total is preferably 0 to 40.
  • silyl group-containing acrylic polymer (2) can be obtained by the first synthesis method or the second synthesis method described below.
  • a silyl group-containing acrylic polymer (2) comprises (A) a silyl group-containing acrylic monomer, (B) methyl methacrylate (MMA), (D) C—OH.
  • a monomer component comprising a group-containing acrylic monomer and, if necessary, (C) another copolymerizable acrylic monomer, peroxides such as dicumyl peroxide, benzoyl peroxide, or 2, 2
  • a radical polymerization initiator selected from the group consisting of azo compounds such as ′ -azobis (isobutyronitrile) is added and heated (40 to 150 ° C., particularly 50 to 120 ° C., 1 to 10 hours, particularly 3 to 8 hours), it can be easily obtained.
  • Second synthesis method (i) Synthesis of first acrylic polymer (intermediate) (B) Methyl methacrylate (MMA) and (D) C—OH group-containing acrylic monomer, If necessary, (C) another copolymerizable acrylic monomer is copolymerized.
  • the solution containing the monomer is selected from the group consisting of peroxides such as dicumyl peroxide and benzoyl peroxide or azo compounds such as 2,2′-azobis (isobutyronitrile).
  • the first acrylic polymer (intermediate) is obtained.
  • (B) methyl methacrylate (MMA) and (C) other copolymerizable acrylic monomers have a silyl group-containing acrylic polymer (Mole ratio of polymer units based on each) finally obtained ( Since it becomes equal to the molar ratio of each polymerization unit in 2), these monomers are blended so as to have a copolymer composition in the silyl group-containing acrylic polymer (2).
  • MMA methyl methacrylate
  • (C) other copolymerizable acrylic monomers have a silyl group-containing acrylic polymer (Mole ratio of polymer units based on each) finally obtained ( Since it becomes equal to the molar ratio of each polymerization unit in 2), these monomers are blended so as to have a copolymer composition in the silyl group-containing acrylic polymer (2).
  • the C—OH group-containing acrylic monomer has a polymerization unit based on the C—OH group-containing acrylic polymer (2) to be finally obtained and a molar ratio of the C—OH group-containing polymerization unit in the desired silyl group-containing acrylic polymer (2). It mix
  • MMA methyl methacrylate
  • D C—OH group-containing polymer units based on C—OH group-containing acrylic monomers
  • C other copolymerizable acrylic systems
  • Such a first acrylic polymer is also commercially available.
  • a commercially available product such as a hydroxyalkyl group-containing acrylic polymer JR4811 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymerization based on methyl methacrylate (MMA)).
  • the molar ratio of the units, polymer units based on lauryl methacrylate (LMA), polymer units based on n-butyl methacrylate (BMA) and polymer units based on hydroxyethyl methacrylate (HEMA) is 67: 3: 21: 9, Mw 16,000. ) Can be used.
  • the weight average molecular weight Mw of JR4811 is obtained by gel permeation chromatography (GPC, HLC-8220GPC manufactured by Tosoh Corporation, RI detection, column: TSK guard column SuperHZ-L + TSKgel SuperHZ4000 + HZ3000 + HZ2500 + HZ2000, eluent: THF).
  • the polymerization unit and the molar ratio thereof were determined by dissolving in deuterated chloroform and nuclear magnetic resonance analysis ( 13 C-NMR, ECA600 manufactured by JEOL Ltd.).
  • the first acrylic polymer is reacted with at least one (preferably one) hydrolyzable silyl group and / or SiOH group and C—OH group.
  • a compound having at least one (preferably one) functional group possible is reacted.
  • the functional group capable of reacting with the C—OH group include an isocyanate group and an epoxy group, and an isocyanate group is preferable from the viewpoint of easy reaction control.
  • sil group-containing isocyanate examples include 3-isocyanatepropyltriethoxysilane, 3 -Isocyanatopropyltrimethoxysilane and the like.
  • a part of the C—OH group-containing polymer unit of the first acrylic polymer is modified to a silyl group-containing polymer unit. That is, in some of the C—OH group-containing polymer units, the isocyanate group of the silyl group-containing isocyanate reacts with the C—OH group of the side chain (urethane reaction), so that the hydrolyzable silyl group and the side chain / Or SiOH groups are introduced.
  • the C—OH group-containing polymerization of the first acrylic polymer A part of the unit is a polymerized unit in which a hydrolyzable silyl group and / or SiOH group is introduced into the side chain via a urethane bond, and the remaining polymerized unit remains as a polymerized unit containing a C—OH group. Can do.
  • a silyl group-containing acrylic polymer (2) is obtained by modifying a part of the C—OH group-containing polymerization unit of the first acrylic polymer to a silyl group-containing polymerization unit.
  • the ratio of polymer units modified to silyl group-containing polymer units by reaction with silyl group-containing isocyanate (hereinafter referred to as the modification rate). It can be 5 to 75 mol%.
  • the modification rate is the ratio of the group reacted with the isocyanate group in the C—OH group of the first acrylic polymer. You can also.
  • methyl methacrylate (MMA), lauryl methacrylate (LMA), n-butyl methacrylate (BMA), and 2-hydroxyethyl methacrylate (HEMA) are converted into 67: 3: 21: 9.
  • MMA methyl methacrylate
  • LMA lauryl methacrylate
  • BMA n-butyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • a hydrolyzable silyl group (triethoxysilyl group) is introduced by being modified by the reaction between the C—OH group and the isocyanate group.
  • the silyl group-containing acrylic polymer (1) and the silyl group-containing acrylic polymer (2) preferably have a weight average molecular weight Mw of 5,000 to 300,000.
  • Mw weight average molecular weight
  • the weight average molecular weight exceeds 300,000, the viscosity of the polymer becomes high, so that it becomes difficult to apply a composition containing the polymer (described later), and an appropriate film thickness may not be obtained.
  • the weight average molecular weight is less than 5,000, the anchor effect with the primer layer is weak and sufficient adhesion is not exhibited.
  • these silyl group-containing acrylic polymers do not contain a polymer unit having an aromatic hydrocarbon group in the side chain. That is, it does not have a structure in which a monomer having an aromatic hydrocarbon group such as an ultraviolet absorbing group is copolymerized.
  • the silyl group-containing acrylic polymer has a structure in which a monomer having an aromatic hydrocarbon group such as an organic ultraviolet absorbing group is copolymerized, the reaction between the organopolysiloxane constituting the hard coat layer and the adhesive layer As a result, the adhesiveness, particularly the weather-resistant adhesiveness, cannot be improved. Further, the familiarity with the primer layer becomes insufficient, and the scratch resistance of the hard coat film cannot be obtained sufficiently.
  • the silyl group-containing acrylic polymer preferably does not contain an aromatic hydrocarbon group such as an ultraviolet absorbing group, but at least one of the primer layer and the hard coat layer described later contains an ultraviolet absorber. By doing, it can have sufficient weather resistance as the whole hard-coat film.
  • the adhesive layer is formed by applying and drying the composition for forming an adhesive layer containing the silyl group-containing acrylic polymer on the primer layer formed on at least one surface of the resin substrate. Further, a hard coat layer containing a cured product of organopolysiloxane as a main component is provided thereon to obtain a resin substrate with a hard coat film. Note that, when the organopolysiloxane is cured in the formation of the hard coat layer, the adhesive layer is also cured, thereby enhancing the adhesion.
  • the silyl group-containing acrylic polymer is reacted by the reaction between hydrolyzable silyl groups and / or SiOH groups contained in the side chain of the polymer, or the polymer. It is considered that a siloxane bond is formed by a reaction between the hydrolyzable silyl group and / or SiOH group possessed by and the hydrolyzable silyl group and / or SiOH group of the organopolysiloxane constituting the hard coat layer. And the silyl group containing acrylic polymer considered that the siloxane bond is formed in this way becomes a main component of the adhesive layer.
  • the composition for forming an adhesive layer applied and dried on the primer layer usually contains a solvent together with the silyl group-containing acrylic polymer.
  • the solvent is not particularly limited as long as it can dissolve the silyl group-containing acrylic polymer stably.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane; esters such as ethyl acetate, butyl acetate and methoxyethyl acetate Methanol; ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methoxyethanol, diacetone alcohol, 2-butoxyethanol, 1-methoxy-2- Examples include alcohols such as propanol and diacetone alcohol; hydrocarbons such as n-hexane, n-heptane, isoctane, benzene, toluene, xylene, gasoline, light oil, and kerosene; acetonitrile, nitromethane, and water.
  • the amount of the solvent is preferably 50 to 10,000 parts by mass, particularly preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the resin component such as the silyl group-containing acrylic polymer.
  • the content of the nonvolatile component (solid content) in the composition for forming an adhesive layer is preferably 0.5 to 75% by mass, particularly 1 to 50% by mass, based on the total amount of the composition. preferable.
  • this composition for contact bonding layer formation may further contain additives, such as a leveling agent, an antifoamer, and a viscosity modifier.
  • the method for applying the adhesive layer forming composition on the primer layer is not particularly limited, and examples thereof include spray coating, dip coating, flow coating, die coating, and spin coating.
  • the heating conditions for drying are not particularly limited, but are preferably 50 to 140 ° C. and 5 minutes to 3 hours.
  • the film thickness of the adhesive layer formed on the primer layer using the composition for forming an adhesive layer satisfies the requirements required as an adhesive layer in the resin substrate with a hard coat film finally obtained. If it is, it will not be restrict
  • the film thickness of the adhesive layer is too thin, the weather resistance of the hard coat film as a whole is improved by improving the adhesion with the hard coat layer, weather resistance such as weather cracking The effect of can not be raised enough.
  • the thickness of the adhesive layer is too large, the proportion of the hydrolyzable silyl group and / or SiOH group in the silyl group-containing acrylic polymer that constitutes the adhesive layer is reduced. The proportion of bonding within the adhesive layer increases. As a result, stress is generated due to excessive bonding inside the adhesive layer, which causes weathering cracks.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 5 ⁇ m in the adhesive layer containing the silyl group-containing acrylic polymer (1) as a main component.
  • the thickness is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.2 ⁇ m to 2 ⁇ m. This film thickness means the thickness when the film is formed alone on a substrate such as a resin substrate.
  • the resin substrate with a hard coat film of the present invention has a hard coat layer containing a cured product of organopolysiloxane as a main component on the adhesive layer.
  • the hard coat layer according to the present invention contains a cured product of organopolysiloxane as a main component.
  • the organopolysiloxane that forms the cured product may be a curable organopolysiloxane.
  • it can be used without particular limitation.
  • Organopolysiloxane is composed of silicon-containing bond units called M units, D units, T units, and Q units.
  • the curable organopolysiloxane used for the formation of the hard coat layer of the present invention is an oligomeric polymer mainly composed of T units or Q units, a polymer composed only of T units, and Q units. There are polymers composed of only T and Q units. These polymers may further contain a small amount of M units and D units.
  • the T unit has one silicon atom, one hydrogen atom or monovalent organic group bonded to the silicon atom, and an oxygen atom bonded to another silicon atom or It is a unit having three functional groups capable of bonding to other silicon atoms.
  • the monovalent organic group bonded to the silicon atom is a monovalent organic group in which the atom bonded to the silicon atom is a carbon atom.
  • the functional group that can be bonded to another silicon atom is a hydroxyl group or a hydrolyzable group that becomes a hydroxyl group by hydrolysis.
  • the total number of oxygen atoms bonded to other silicon atoms and functional groups that can bond to other silicon atoms is three, and the number of functional groups that can bond to oxygen atoms bonded to other silicon atoms and other silicon atoms is different.
  • the T unit is classified into three types of units called T1, T2, and T3.
  • T1 has one oxygen atom bonded to another silicon atom
  • T2 has two oxygen atoms
  • T3 has three oxygen atoms.
  • an oxygen atom bonded to another silicon atom is represented by O *
  • a monovalent functional group that can be bonded to another silicon atom is represented by Z.
  • O * representing an oxygen atom bonded to another silicon atom is an oxygen atom bonded between two silicon atoms, and is an oxygen atom in a bond represented by Si—O—Si. Accordingly, one O * exists between the silicon atoms of two silicon-containing bond units. In other words, O * represents an oxygen atom shared by two silicon atoms of two silicon-containing bond units. In the chemical formula of the silicon-containing bond unit described later, it is expressed as O * is bonded to one silicon atom, but this O * is an oxygen atom shared with the silicon atom of another silicon-containing bond unit. It does not mean that two silicon-containing bond units are bonded by a bond represented by Si—O * —O * —Si.
  • the M unit is a unit having 3 organic groups and 1 O *
  • the D unit is a unit having 2 organic groups and 2 O * (or 1 O * and 1 Z group)
  • a Q unit Is a unit having 0 organic groups and 4 O * (or 4 O * 1 to 3 and 3 to 1 Z groups).
  • T monomer Monomers that form M units, D units, and Q units are also referred to as M monomers, D monomers, and Q monomers.
  • the monomer is represented by (R′—) a Si (—Z) 4-a .
  • a represents an integer of 0 to 3
  • R ′ represents a hydrogen atom or a monovalent organic group
  • Z represents a monovalent functional group capable of bonding to a hydroxyl group or another silicon atom.
  • the Z group is usually a hydrolyzable group.
  • R ′ is preferably in the same category as preferable R described later.
  • the curable organopolysiloxane is obtained by a reaction in which a part of the Z group of the monomer is converted to O * .
  • the organopolysiloxane is a copolymer comprising two or more silicon-containing bond units, these copolymers are usually obtained from a mixture of the corresponding monomers.
  • the Z group of the monomer is a hydrolyzable group, the Z group is converted into a hydroxyl group by a hydrolysis reaction, and then two silicon atoms are converted by a dehydration condensation reaction between two hydroxyl groups bonded to separate silicon atoms. Bonding through an oxygen atom (O * ).
  • hydroxyl groups (or Z groups that have not been hydrolyzed) remain, and when the curable organopolysiloxane is cured, these hydroxyl groups and Z groups react and cure as described above.
  • the cured product of the curable organopolysiloxane is a three-dimensionally crosslinked polymer, and the cured product of the curable organopolysiloxane having many T units and Q units is a cured product having a high crosslinking density.
  • the Z group of the curable organopolysiloxane is converted to O * , but a part of the Z group (particularly hydroxyl group) remains and is considered to be a cured product having a hydroxyl group.
  • the curable organopolysiloxane is cured at a high temperature, a cured product in which almost no hydroxyl groups remain may be obtained.
  • the Z group of the monomer is a hydrolyzable group
  • examples of the Z group include an alkoxy group, a chlorine atom, an acyloxy group, and an isocyanate group.
  • a monomer in which the Z group is an alkoxy group is used as the monomer.
  • the alkoxy group is a hydrolyzable group having a relatively low reactivity compared to a chlorine atom, etc., and in the curable organopolysiloxane obtained using a monomer in which the Z group is an alkoxy group, There are often unreacted alkoxy groups.
  • the Z group of the monomer is a hydrolyzable group having a relatively high reactivity (for example, a chlorine atom)
  • most of the Z groups in the curable organopolysiloxane obtained using the monomer are hydroxyl groups. Therefore, in a normal curable organopolysiloxane, the Z group in each unit constituting it is often composed of a hydroxyl group or a hydroxyl group and an alkoxy group.
  • curable organopolysiloxanes having T units as main silicon-containing bond units are preferably used.
  • curable organopolysiloxane is simply referred to as organopolysiloxane.
  • organopolysiloxane (T) refers to an M unit, a D unit, a T unit, and An organopolysiloxane in which the ratio of the number of T units to the total number of Q units is from 50 to 100%.
  • an organopolysiloxane having a ratio of the number of T units of from 70 to 100% is particularly preferred. Uses an organopolysiloxane having a T-unit ratio of 90 to 100%. Moreover, as other units contained in a small amount other than T units, D units and Q units are preferable, and Q units are particularly preferable.
  • the ratio of the number of M units, D units, T units, and Q units in the organopolysiloxane can be calculated from the value of the peak area ratio by 29 Si-NMR.
  • the organopolysiloxane (T) preferably used in the present invention is an organopolysiloxane having T units represented by the following T1 to T3.
  • T1 R—Si (—OX) 2 (—O * —)
  • T2 R—Si (—OX) (— O * ⁇ ) 2
  • T3 R—Si (—O * ⁇ ) 3
  • R represents a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms
  • X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • O * represents an oxygen atom connecting silicon atoms
  • R in the above chemical formula is not limited to one type, and T1, T2, and T3 may each include a plurality of types of R.
  • —OX represents a hydroxyl group or an alkoxy group.
  • -OX may be the same or different between T1 and T2.
  • the two —OX in T2 may be different.
  • one may be a hydroxyl group and the other may be an alkoxy group.
  • the alkoxy groups may be different alkoxy groups. However, as described later, usually, the two alkoxy groups are the same alkoxy group.
  • T0 The T unit having no oxygen atom (O * ) for bonding two silicon atoms and having only three —OX is hereinafter referred to as T0.
  • T0 actually corresponds to an unreacted T monomer contained in the organopolysiloxane and is not a silicon-containing bond unit. This T0 is measured in the same manner as T1 to T3 in the analysis of units of T1 to T3.
  • T0 to T3 in the organopolysiloxane can be analyzed by measuring the bonding state of silicon atoms in the organopolysiloxane by nuclear magnetic resonance analysis ( 29 Si-NMR). The ratio of the number of T0 to T3 is determined from the peak area ratio of 29 Si-NMR. -OX in the organopolysiloxane molecule can be analyzed by infrared absorption analysis. The ratio of the number of hydroxyl groups bonded to silicon atoms and the number of alkoxy groups is determined from the peak area ratio of the infrared absorption peaks of the two.
  • the weight average molecular weight Mw, the number average molecular weight Mn, and the dispersity Mw / Mn of the organopolysiloxane are values measured by gel permeation chromatography using polystyrene as a standard substance.
  • the characteristics of such an organopolysiloxane do not refer to the characteristics of one molecule but are determined as the average characteristics of each molecule.
  • T two or more different T1, T2, and T3 may exist in each molecule.
  • two or more types of T2 with different R may exist.
  • Such organopolysiloxanes are obtained from a mixture of two or more T monomers.
  • an organopolysiloxane obtained from a mixture of two or more T monomers having different R it is considered that two or more T1, T2, and T3 having different R exist.
  • the ratio of the number of different R in the organopolysiloxane obtained from a mixture of a plurality of T monomers having different R reflects the composition ratio of the T monomer mixture having different R as a whole T unit.
  • the ratio of the number of units with different R in each of T1, T2, and T3 does not necessarily reflect the composition ratio of T monomer mixtures with different R. This is because the reactivity of the T monomer, T1, and T2 may differ depending on the difference in R even if the three —OXs in the T monomer are the same.
  • the organopolysiloxane (T) is preferably produced from at least one T monomer represented by R—Si (—OY) 3 .
  • R is the same as R described above, and Y represents an alkyl group having 1 to 6 carbon atoms.
  • Y may be a substituted alkyl group such as an alkoxy-substituted alkyl group in addition to an unsubstituted alkyl group.
  • Three Y in one molecule may be different. However, usually three Y are the same alkyl group.
  • Y is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms. Specific examples of Y include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a t-butyl group, and a 2-methoxyethyl group.
  • R is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms.
  • the organic group means an organic group in which the atom bonded to the silicon atom is a carbon atom as described above.
  • Examples of the unsubstituted monovalent organic group include hydrocarbon groups such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and an aralkyl group. These hydrocarbon groups include an alkyl group having 1 to 10 carbon atoms, an alkenyl group or alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number 7-10 aralkyl groups are preferred.
  • Examples of the substituted monovalent organic group include a hydrocarbon group in which a ring hydrogen atom such as a cycloalkyl group, an aryl group, and an aralkyl group is substituted with an alkyl group, and the hydrogen atom of the hydrocarbon group is a halogen atom or a functional group And a substituted organic group substituted with a functional group-containing organic group.
  • a hydroxyl group, mercapto group, carboxyl group, epoxy group, amino group, cyano group and the like are preferable.
  • an alkyl group having a chlorine atom or a fluorine atom such as a chloroalkyl group or a polyfluoroalkyl group is preferable.
  • the functional group-containing organic group include an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted aminoalkyl group. preferable.
  • the T monomer having a substituted organic group substituted with a functional group or a functional group-containing organic group includes a category of compounds called silane coupling agents.
  • substituted organic group examples include the following organic groups. 3-chloropropyl group, 3,3,3-trifluoropropyl group, 3-mercaptopropyl group, p-mercaptomethylphenylethyl group, 3-acryloyloxypropyl group, 3-methacryloyloxypropyl group, 3-glycidoxy Propyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, 2-cyanoethyl Group.
  • a particularly preferred monovalent organic group as R is an alkyl group having 1 to 4 carbon atoms.
  • the organopolysiloxane (T) is preferably an organopolysiloxane obtained by using a T monomer having an alkyl group having 1 to 4 carbon atoms alone or two or more thereof.
  • An organopolysiloxane obtained by using one or more T monomers having an alkyl group having 1 to 4 carbon atoms and a small amount of other T monomers as the organopolysiloxane (T) is also preferable.
  • the proportion of other T monomers is preferably 30 mol% or less, particularly preferably 15 mol% or less, based on the total amount of T monomers.
  • a T monomer having a substituted organic group substituted with a functional group, a functional group-containing organic group, or the like in a category called a silane coupling agent is preferable.
  • T monomer having an alkyl group having 1 to 4 carbon atoms include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. In particular, methyltrimethoxysilane or ethyltrimethoxysilane is preferable.
  • T monomer having a substituted organic group and the like include the following compounds.
  • R-Si (-OY) other than T monomer represented by 3 (R'-) a Si (-Z ) T monomers represented by 4-a (a 3) , for example, methyltrichlorosilane, Examples thereof include ethyltrichlorosilane, phenyltrichlorosilane, 3-glycidoxypropyltrichlorosilane, methyltriacetoxysilane, and ethyltriacetoxysilane.
  • two R ′ may be the same or different.
  • an alkyl group having 1 to 4 carbon atoms is preferred.
  • one R ′ is an alkyl group having 1 to 4 carbon atoms
  • the other R ′ is a substituted organic group substituted with the functional group or the functional group-containing organic group.
  • the Z group is preferably an alkoxy group having 1 to 4 carbon atoms, an acetoxy group, or the like.
  • Examples of the D monomer include dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiacetoxysilane, 3-chloropropylmethyldimethoxysilane, 3, 3, 3-trifluoropropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldilane, 3-aminopropylmethyldilane, 3-aminopropylmethyldilane. Examples include ethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-
  • the four Z groups may be different but are usually the same.
  • the Z group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.
  • Examples of the Q monomer include tetramethoxysilane, tetraethoxysilane, tetra n-propoxy silane, tetra n-butoxy silane, tetra sec-butoxy silane, and tetra t-butoxy silane.
  • the organopolysiloxane (T) used in the present invention is obtained by subjecting the above T monomer and the like to partial hydrolysis condensation. Usually, this reaction is performed by heating T monomer or the like and water in a solvent. A catalyst is preferably present in the reaction system.
  • the target organopolysiloxane can be produced by adjusting the reaction conditions such as the type of monomer, the amount of water, the heating temperature, the type and amount of catalyst, and the reaction time. In some cases, a commercially available organopolysiloxane can be used as it is as the target organopolysiloxane, or the desired organopolysiloxane can be produced using a commercially available organopolysiloxane.
  • Acid catalysts include inorganic acids 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, p- An organic acid such as toluenesulfonic acid may be mentioned. In particular, acetic acid is preferred.
  • the solvent is preferably a hydrophilic organic solvent, and particularly preferably an alcohol solvent.
  • alcohol solvents examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, diacetone alcohol, 2-butoxyethanol and the like. It is done.
  • the reaction temperature can be reacted at room temperature when a catalyst is present. Usually, an appropriate temperature is adopted from the reaction temperature of 20 to 80 ° C. according to the purpose.
  • the hydrolysis condensation reaction is a reaction in which T1 is generated from T0 (T monomer), T2 is generated from T1 and T3 is generated from T2.
  • Condensation reaction in which at least one hydrolyzable group is converted to a hydroxyl group from T0 to T1
  • the reaction rate of the condensation reaction in which T3 is generated from the reaction becomes slower in this order. Even considering the hydrolysis reaction of the hydrolyzable group, it is considered that the peak of the abundance of each unit moves from T0 to T3 as the reaction proceeds.
  • the organopolysiloxane (a) has a small amount of T0 and T1, and the ratio of the amounts of T2 and T3 is within a specific range.
  • Some relatively high molecular weight organopolysiloxanes, and such organopolysiloxanes can be produced by selecting relatively mild reaction conditions.
  • the reactivity of the above condensation reaction varies depending on R, and when R is different, the reactivity of the hydroxyl group also varies.
  • R for example, when R is an alkyl group, the smaller the number of carbon atoms in the alkyl group), the higher the reactivity of the hydroxyl group. Accordingly, it is preferable to select the T monomer in consideration of the relationship between the reactivity of the hydrolyzable group and the reactivity of the hydroxyl group.
  • the rate of hydrolysis reaction of a hydrolyzable group to a hydroxyl group varies depending on the type of hydrolyzable group, and it is preferable to consider the relationship with the rate of condensation reaction. For example, when the OX group of T2 is an alkoxy group, if the rate of the hydrolysis reaction is too slow, T2 in which the OX group is a hydroxyl group decreases. Similarly, when the rate of the hydrolysis reaction is too slow, T1 in which the OX group is a hydroxyl group decreases. For this reason, it is difficult to obtain a high ratio of the amount of hydroxyl groups to alkoxy groups in the organopolysiloxane.
  • the alkoxy group which is an OX group is preferably a highly reactive alkoxy group, that is, an alkoxy group having a small number of carbon atoms, and most preferably a methoxy group.
  • a highly reactive alkoxy group that is, an alkoxy group having a small number of carbon atoms, and most preferably a methoxy group.
  • the hard coat layer in the resin substrate with a hard coat film of the present invention may contain, as a main component, a cured product obtained by using one of the curable organopolysiloxanes (T) thus obtained. It is also possible to contain the hardened
  • a composition hereinafter referred to as “hard coat” that is usually used and contains a material before curing of the components constituting the hard coat layer. A composition for forming a layer ") is prepared and used.
  • the curable organopolysiloxane (T) preferably used in the present invention is also incorporated into such a hard coat layer-forming composition in the production process so as to be contained as a cured product in the obtained hard coat layer. It becomes possible.
  • a particularly preferred combination of organopolysiloxane (T) from the viewpoint of scratch resistance and weather resistance is a combination of organopolysiloxane (a) and organopolysiloxane (b) described below, but curing used in the present invention.
  • the functional organopolysiloxane is not limited to these. Further, the organopolysiloxane (a) and the organopolysiloxane (b) are not precluded from being used in the present invention alone as the organopolysiloxane (T).
  • the weight average molecular weight of the organopolysiloxane (a) is 800 to 8,000.
  • the organopolysiloxane (a) does not substantially contain T0 which is a T monomer.
  • (T2 + T3) / (T1 + T2 + T3) is preferably in the range of 0.85 to 1.00. More preferably, it is 90 or more and less than 1.00. For T3 / T2, the preferred range is 2.0 to 4.0.
  • the organopolysiloxane (a) and the organopolysiloxane (b) described later can be obtained.
  • the composition for forming a hard coat layer for forming the hard coat layer according to the present invention it improves the scratch resistance and weather resistance of the hard coat layer obtained by curing them. It becomes possible.
  • (B) / (A) in the organopolysiloxane (a) is a parameter indicating condensation reactivity. The larger this value, that is, the greater the proportion of hydroxyl groups compared to the alkoxy groups, the greater the organopolysiloxane (a).
  • organopolysiloxane (b) is used in combination in a composition for forming a hard coat layer, the curing reaction during formation of the hard coat layer is promoted.
  • the alkoxy group remaining unreacted during the formation of the hard coat layer may cause a decrease in the scratch resistance of the hard coat layer, and if post-curing progresses, it may cause micro cracks.
  • (B) / (A) in the organopolysiloxane (a) is 12.0 or more, preferably 16.0 or more. Note that (A) may be zero.
  • the weight average molecular weight of the organopolysiloxane (a) is 800 to 8,000, preferably 1,000 to 6,000.
  • the hard coat layer for forming the hard coat layer according to the present invention by combining the organopolysiloxane (a) and the organopolysiloxane (b).
  • the scratch resistance and weather resistance of the resulting hard coat layer can be sufficiently improved.
  • the organopolysiloxane (a) used in the hard coat layer forming composition for forming a hard coat layer having particularly excellent scratch resistance all T It is preferable that 70% by mass or more of the monomer is methyltrialkoxysilane, and preferably the alkoxy group has 1 to 4 carbon atoms. However, a small amount of a T monomer other than methyltrialkoxysilane can be used in combination for the purpose of improving the adhesion, hydrophilicity, water repellency and the like.
  • a T monomer or the like is subjected to a hydrolysis condensation reaction in a solvent in the presence of an acid catalyst.
  • the water required for the hydrolysis is usually 1 to 10 mol, preferably 1.5 to 7 mol, more preferably 3 to 5 mol, with respect to 1 mol of the monomer.
  • the monomer is hydrolyzed and condensed, it can also be carried out in a reaction system in which colloidal silica (described later) is present.
  • colloidal silica described later
  • water-dispersed colloidal silica is used as the colloidal silica, water is supplied from this dispersion. Is done.
  • the amount of the acid catalyst used is preferably from 0.1 to 50 parts by weight, particularly preferably from 1 to 20 parts by weight, based on 100 parts by weight of the monomer.
  • the solvent the alcohol solvent is preferable, and from the viewpoint of good solubility of the resulting organopolysiloxane (a), specifically, methanol, ethanol, 2-propanol, 1-butanol, or 2-butanol is used. Particularly preferred.
  • the reaction temperature is 20 to 40 ° C., and the reaction time is 1 hour to several days.
  • the hydrolysis and condensation reaction of the monomer is an exothermic reaction, it is preferable that the temperature of the system does not exceed 60 ° C. It is also preferable to allow the hydrolysis reaction to proceed sufficiently under such conditions, and then to proceed the condensation reaction at 40 to 80 ° C. for 1 hour to several days in order to stabilize the resulting organopolysiloxane.
  • Organopolysiloxane (a) can also be produced from commercially available organopolysiloxane. Since the commercially available organopolysiloxane is usually an organopolysiloxane having a higher proportion of alkoxy groups than the hydroxyl group, it is particularly similar to the desired organopolysiloxane (a) except for the above (B) / (A). It is preferable to produce a organopolysiloxane (a) by using a commercially available organopolysiloxane and increasing the proportion of hydroxyl groups by hydrolysis reaction.
  • organopolysiloxane examples include the following organopolysiloxanes, which are partially hydrolyzed condensates of methyltrimethoxysilane.
  • the notation “ND” indicates that it is below the detected amount when the peak area ratio of 29 Si-NMR is measured using a nuclear magnetic resonance analyzer, manufactured by JEOL Ltd., ECP400 (trade name). (The same applies hereinafter).
  • the organopolysiloxane (a) When producing the organopolysiloxane (a) from the above-mentioned commercially available organopolysiloxane, it is preferable to hydrolyze the alkoxy group of the commercially available organopolysiloxane mainly in the presence of an acid catalyst. For example, 0 to 10 times the amount (mass) of a solvent is added to a commercially available organopolysiloxane, stirred well, and then an acid aqueous solution of about 0.1 to 70% by mass is added to obtain 15 to 80 ° C., preferably 20 Examples of the method include stirring at a temperature of ⁇ 70 ° C. for 1 to 24 hours. As the solvent to be used, an aqueous solvent can be used, and in addition, the above alcohol solvent to which water has been added can also be used.
  • organopolysiloxane (b) used in combination with the organopolysiloxane (a) in the composition for forming a hard coat layer for forming the hard coat layer according to the present invention is a weight average molecular weight of the organopolysiloxane (a).
  • the organopolysiloxane (b) is an organopolysiloxane having a smaller weight average molecular weight than the organopolysiloxane (a) to be combined, and has the T1 to T3 units.
  • the ratio of the numbers of T1, T2, and T3, the ratio of T3 / T2, and the ratio of (B) / (A) are not particularly limited.
  • the weight average molecular weight Mw of the organopolysiloxane (b) is preferably 1/8 to 1 / 1.5 times that of the combined organopolysiloxane (a).
  • the weight average molecular weight of the organopolysiloxane (b) exceeds 1 / 1.5 times the weight average molecular weight of the organopolysiloxane (a)
  • the weight average molecular weight of the organopolysiloxane (a) is changed to the organopolysiloxane ( If the weight average molecular weight of b) is less than 1.5 times, the toughness of the resulting hard coat layer is lowered, which causes cracking.
  • the weight average molecular weight of the organopolysiloxane (b) is less than 1/10 times the weight average molecular weight of the organopolysiloxane (a), in other words, the weight average molecular weight of the organopolysiloxane (a) is the organopolysiloxane (b).
  • the hard coat layer obtained has low scratch resistance, and a hard coat layer having sufficient scratch resistance cannot be obtained.
  • a large proportion of T0 and T1 in the organopolysiloxane (b) generally indicates that the hydrolysis reaction or condensation reaction of the raw material monomer was insufficient when the organopolysiloxane was produced.
  • organopolysiloxane (b) when the ratio of T0 and T1 is large, a hard coat layer forming composition containing the organopolysiloxane (b) and the organopolysiloxane (a) is used. Cracks tend to increase during thermosetting when forming. In general, when the organopolysiloxane is produced, if the condensation reaction of the raw material monomer is allowed to proceed excessively, the ratio of T3 of the resulting organopolysiloxane increases.
  • a hard coat layer forming composition containing the organopolysiloxane (b) and the organopolysiloxane (a) is used to form a hard coat layer.
  • an appropriate cross-linking reaction becomes difficult, so that a hard coat layer may not be formed, and a hard coat layer having sufficient scratch resistance may not be obtained.
  • the organopolysiloxane (b) can be produced from a T monomer or the like in the same manner as the organopolysiloxane (a).
  • Commercially available organopolysiloxane can be used as organopolysiloxane (b) as it is.
  • Examples of commercially available organopolysiloxanes that can be used as the organopolysiloxane (b) include the following organopolysiloxanes.
  • the notation of “trace” is 0.01 or more and 0.25 or less when the peak area ratio of 29 Si-NMR is measured using a nuclear magnetic resonance analyzer, manufactured by JEOL Ltd., ECP400 (trade name). (The same applies hereinafter).
  • the ratio of the content of the organopolysiloxane (b) to the organopolysiloxane (a) is as follows:
  • the mass ratio is preferably 1.5 to 30 times, and more preferably 2 to 15 times.
  • the organopolysiloxane three-dimensional crosslinked structure formed by the curing reaction becomes an organopolysiloxane.
  • the component (a) organopolysiloxane is partially incorporated into the main three-dimensional crosslinked structure, and the resulting hard coat layer can have good weather resistance and scratch resistance.
  • composition for forming a hard coat layer In order to form the hard coat layer of the resin substrate with a hard coat film of the present invention, it contains the above curable organopolysiloxane, preferably organopolysiloxane (T).
  • a composition for forming a hard coat layer is used.
  • the content of the organopolysiloxane in the composition for forming a hard coat layer is preferably 50 to 100% by mass with respect to the total amount of the composition excluding the solvent (hereinafter referred to as “nonvolatile component” as necessary) More preferably, it is 60 to 95% by mass.
  • the “nonvolatile component” means a mass% calculated based on a mass change of a residual component after being held at 150 ° C. for 45 minutes.
  • the hard coat layer forming composition used in the present invention may contain various additives in addition to the organopolysiloxane.
  • the hard coat layer preferably contains fine silica particles, and therefore, the hard coat containing the fine silica particles A layer forming composition is preferably used.
  • blend colloidal silica refers to silica fine particles dispersed in water or an organic solvent such as methanol, ethanol, isobutanol, or propylene glycol monomethyl ether.
  • the silica fine particles can be blended with the raw material monomer in the process of producing the organopolysiloxane.
  • organopolysiloxane in a reaction system containing colloidal silica, an organopolysiloxane containing silica fine particles can be obtained.
  • a T monomer and, if necessary, water or an acid catalyst are added to colloidal silica, and the organopolysiloxane can be produced as described above in a dispersion medium of colloidal silica.
  • a composition for forming a hard coat layer used in the present invention containing silica fine particles can be produced.
  • the silica fine particles contained in the hard coat layer forming composition according to the present invention preferably have an average particle size (BET method) of 1 to 100 nm. When the average particle diameter exceeds 100 nm, the particles diffusely reflect light, and thus the haze (cloudiness value) of the resulting hard coat layer increases, which may be undesirable in terms of optical quality. Further, the average particle size is particularly preferably 5 to 40 nm. This is for imparting scratch resistance to the hard coat layer and maintaining the transparency of the hard coat layer. Moreover, although colloidal silica can use both a water dispersion type and an organic solvent dispersion type, it is preferable to use a water dispersion type.
  • colloidal silica dispersed in an acidic aqueous solution.
  • the colloidal silica may contain inorganic fine particles other than silica fine particles such as alumina sol, titania sol, and ceria sol.
  • the content of silica fine particles in the composition for forming a hard coat layer used in the present invention is preferably 1 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the composition (nonvolatile components) excluding the solvent. Is more preferred.
  • the content of the silica fine particles in the nonvolatile component in the composition for forming a hard coat layer used in the present invention is less than 1% by mass, sufficient scratch resistance may not be ensured in the obtained hard coat layer, and the content is If it exceeds 50% by mass, the proportion of the organopolysiloxane in the non-volatile component becomes too low, and it becomes difficult to form a hard coat layer by thermosetting the organopolysiloxane, and cracks are generated in the resulting hard coat layer. There is a risk that the transparency of the hard coat layer is reduced due to aggregation of the fine particles.
  • the composition for forming a hard coat layer used in the present invention may further contain additives such as an antifoaming agent and a viscosity modifier for the purpose of improving the coating property, and for the purpose of improving the adhesion to the adhesive layer.
  • additives such as an antifoaming agent and a viscosity modifier for the purpose of improving the coating property, and for the purpose of improving the adhesion to the adhesive layer.
  • an additive such as an adhesion-imparting agent may be included, and a leveling agent may be included as an additive for the purpose of improving the coatability and the smoothness of the resulting coating film.
  • the amount of these additives is preferably 0.01 to 2 parts by mass for each additive component with respect to 100 parts by mass of the organopolysiloxane.
  • the composition for forming a hard coat layer used in the present invention may contain a dye, a pigment, a filler and the like as long as the object of the present invention is not impaired.
  • the hard coat layer forming composition used in the present invention may further contain a curing catalyst.
  • Curing catalysts include aliphatic carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, succinic acid, etc.), alkali metal salts such as lithium salt, sodium salt, potassium salt; benzyltrimethylammonium salt, tetramethylammonium salt Quaternary ammonium salts such as salts and tetraethylammonium salts; metal alkoxides and chelates such as aluminum, titanium and cerium; ammonium perchlorate, ammonium chloride, ammonium sulfate, sodium acetate, imidazoles and their salts, ammonium trifluoromethylsulfonate, Bis (tolufluoromethylsulfonyl) bromomethylammonium and the like can be mentioned.
  • the blending amount of the curing catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the organopolysiloxane.
  • the content of the curing catalyst is less than 0.01 parts by mass, it is difficult to obtain a sufficient curing rate.
  • the content is more than 10 parts by mass, the storage stability of the composition for forming a hard coat layer is reduced, or a precipitate is formed. There are things to do.
  • the hard coat layer forming composition used in the present invention preferably further contains an ultraviolet absorber in order to suppress yellowing of the resin substrate.
  • an ultraviolet absorber benzophenone UV absorbers, benzotriazole UV absorbers, benzimidazole UV absorbers, cyanoacrylate UV absorbers, salicylate UV absorbers, benzylidene malonate UV absorbers, triazine UV An absorbent etc. are mentioned. These ultraviolet absorbers may be used alone or in combination of two or more. Moreover, in order to suppress the bleeding out of the said ultraviolet absorber from a hard-coat layer, you may use the ultraviolet absorber which has a trialkoxy silyl group.
  • Ultraviolet absorbers having trialkoxysilyl groups are converted into hydroxyl groups by hydrolysis reaction during the hard coat layer formation by thermosetting organopolysiloxane, and then incorporated into the hard coat layer by dehydration condensation reaction. Bleed out of the agent from the hard coat layer can be suppressed.
  • Specific examples of such trialkoxysilyl groups include trimethoxysilyl groups and triethoxysilyl groups.
  • the content of the ultraviolet absorber in the hard coat layer forming composition is preferably 0.1 to 30 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the organopolysiloxane. Is particularly preferred.
  • the hard coat layer-forming composition is adjusted to pH 3.5 to 6.0 in order to prevent gelation of the hard coat layer-forming composition at room temperature and increase storage stability. It is preferable to adjust to 3.5 to 5.0. Under conditions where the pH is 2.0 or lower or 7.0 or higher, the hydroxyl group bonded to the silicon atom is extremely unstable, and thus is not suitable for storage.
  • the pH range in the composition for forming a hard coat layer used in the present invention is the type and weight average molecular weight of the acrylic polymer used for the primer layer, the type and blending amount of the UV absorber, and the silyl group content of the composition for forming the adhesive layer.
  • the preferred pH range can be generally from 3.5 to 4.5.
  • Measures for pH adjustment include addition of acid, adjustment of the content of the curing catalyst, and the like.
  • Acids include inorganic acids 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, p-toluene
  • organic acids such as sulfonic acid, among which acetic acid or hydrochloric acid is preferable.
  • the pH itself is adjusted in consideration of this point because it exhibits the same action as the acid itself.
  • the composition for forming a hard coat layer used in the present invention is usually prepared in a form in which organopolysiloxane as an essential component and various additives as optional components are dissolved and dispersed in a solvent. It is necessary for all the non-volatile components in the hard coat layer forming composition to be stably dissolved and dispersed in a solvent.
  • the solvent contains at least 20% by mass, preferably 50% by mass or more of alcohol. .
  • alcohols used in such solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, and 2-ethoxyethanol.
  • Diacetone alcohol, 2-butoxyethanol and the like are preferable.
  • alcohol having a boiling point of 80 to 160 ° C. is preferable from the viewpoint of good solubility of the organopolysiloxane and good coating property.
  • ethanol 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, diacetone alcohol, or 2 -Butoxyethanol is preferred.
  • the solvent used in the composition for forming a hard coat layer according to the present invention includes, for example, lower alcohol generated by hydrolyzing a raw material monomer such as an alkyltrialkoxysilane when an organopolysiloxane is produced.
  • a raw material monomer such as an alkyltrialkoxysilane when an organopolysiloxane is produced.
  • the dispersed organic solvent is also included.
  • a solvent other than the above a solvent other than alcohol that can be mixed with water / alcohol may be used in combination.
  • Ketones such as acetone and acetylacetone; esters such as ethyl acetate and isobutyl acetate; ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and diisopropyl ether.
  • the amount of the solvent used in the composition for forming a hard coat layer according to the present invention is preferably 50 to 3,000 parts by mass with respect to 100 parts by mass of all nonvolatile components in the composition for forming a hard coat layer. More preferred is 150 to 2,000 parts by mass.
  • the resin substrate with a hard coat film of the present invention is formed by applying the hard coat layer forming composition of the present invention on the adhesive layer obtained above. It can be produced by forming a hard coat layer by curing a curable compound containing organopolysiloxane as a main component in the coating film.
  • the method for applying the composition for forming a hard coat layer is not particularly limited, and examples thereof include ordinary coating methods such as spray coating, dip coating, flow coating, die coating, and spin coating. It is preferable to appropriately adjust the viscosity, solid content concentration and the like of the composition for forming a hard coat layer depending on the coating method.
  • the composition for forming a hard coat layer applied on the adhesive layer is usually cured by heating after the solvent is dried and removed under normal temperature to a temperature lower than the heat deformation temperature of the resin substrate, the primer layer, and the adhesive layer.
  • the drying conditions for the solvent include conditions of 20 to 60 ° C. and 15 minutes to 10 hours. Moreover, you may use vacuum drying etc., adjusting a pressure reduction degree.
  • the thermosetting reaction is preferably performed at a high temperature within a range in which there is no problem in the heat resistance of the resin substrate, the primer layer, and the adhesive layer because the curing can be completed more quickly.
  • the curing temperature is preferably 50 to 200 ° C, particularly preferably 80 to 160 ° C, and particularly preferably 90 ° C to 140 ° C.
  • the curing time is preferably 10 minutes to 4 hours, particularly preferably 20 minutes to 3 hours, particularly preferably 30 minutes to 2 hours.
  • the film thickness of the coating film formed by applying the composition for forming a hard coat layer on the adhesive layer depends on the solid content concentration in the composition. It is preferable to appropriately adjust the solid content concentration so that the film thickness of the hard coat layer formed after the hard coat layer forming composition is cured is in the following range.
  • the film thickness of the hard coat layer is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 1 ⁇ m or more and 10 ⁇ m or less, and more preferably 2 ⁇ m or more and 10 ⁇ m or less as the value of the hard coat layer alone after curing. Is particularly preferred.
  • This film thickness means the thickness when the film is formed alone on a substrate such as a resin substrate.
  • the film thickness of the hard coat layer in the state of the resin substrate with a hard coat film of the present invention is preferably 1 ⁇ m or more and 20 ⁇ m or less.
  • a top coat layer whose main component is SiO 2 is formed on the hard coat layer of the resin substrate with a hard coat film. You may give it.
  • a method for forming the top coat layer whose main component is SiO 2 it is preferable to apply a technique of applying poly (perhydro) silazane on the hard coat layer and curing, or a technique such as vapor deposition or sputtering.
  • the resin substrate with a hard coat film of the present invention has a primer layer, an adhesive layer, and a hard coat layer in this order from the resin substrate side as described above.
  • Such a method for producing a resin substrate with a hard coat film of the present invention comprises at least the following steps (I), (II), and (III).
  • the step (I) is as described in the (2) primer layer, and the step (II) is as described in the (3) adhesive layer.
  • the step (III) is as described in the above (4) hard coat layer.
  • Examples 1 to 11 are examples, and examples 12 to 15 are comparative examples.
  • Mn, Mw, and Mw / Mn of polymethyl methacrylate are gel permeation chromatography (GPC, HLC-8220GPC manufactured by Tosoh Corporation, RI detection, column: TSK guard column Super HZ-L + TSKgel Super HZ 4000 + HZ 3000 + HZ 2500 + THZ 2000), eluent: Sought by.
  • composition for forming adhesive layer was prepared by the method shown below.
  • Mw of the obtained resin etc. was calculated
  • the solution thus obtained was diluted with 1-methoxy-2-propanol to have a nonvolatile content of 10% by mass to obtain an adhesive layer forming composition Ad-1 containing a silyl group-containing acrylic polymer.
  • Mw of the obtained silyl group-containing acrylic polymer was 11,400.
  • the solution thus obtained was diluted with 1-methoxy-2-propanol to a non-volatile content of 10% by mass to obtain an adhesive layer forming composition Ad-2 containing a silyl group-containing acrylic polymer.
  • Mw of the obtained silyl group-containing acrylic polymer was 68,000.
  • the composition was Ad-3.
  • the obtained solution was diluted with 1-methoxy-2-propanol to obtain a non-volatile content of 10% by mass to obtain an adhesive layer forming composition Ad-5 containing a silyl group-containing acrylic polymer.
  • Mw of the obtained silyl group-containing acrylic polymer was 78,000.
  • the obtained solution was diluted with 1-methoxy-2-propanol to obtain a non-volatile content of 10% by mass to obtain an adhesive layer forming composition Ad-6 containing a silyl group-containing acrylic polymer.
  • Mw of the obtained silyl group-containing acrylic polymer was 82,000.
  • a 0.5 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 41 g of diacetone alcohol as a solvent and heated to 80 ° C. under a nitrogen stream.
  • 66 g of the monomer mixed solution and 15 g of the polymerization initiator solution prepared in advance were sequentially added.
  • the remaining monomer mixed solution and the remaining polymerization initiator solution were simultaneously added dropwise at 80 to 90 ° C. over 1.5 hours.
  • the mixture was further stirred at 80 to 90 ° C. for 5 hours.
  • the obtained solution was diluted with 1-methoxy-2-propanol to obtain a non-volatile content of 10% by mass to obtain an adhesive layer forming composition Ad-7 containing a silyl group-containing acrylic polymer.
  • Mw of the obtained silyl group-containing acrylic polymer was 71,000.
  • composition for forming hard coat layer was prepared by the method shown below.
  • the organopolysiloxane was analyzed by the method shown below.
  • 10 g of 1-butanol was added to 10 g and stirred well, and 10 g of acetic acid and 10 g of ion-exchanged water were added. In addition, it was stirred well. This solution was stirred at 40 ° C. for 1 hour to obtain a solution (MSi-1 concentration: 25% by mass) containing component (a) organopolysiloxane MSi-1.
  • MSi-1 was compared with the raw material KR-500 by FT-IR and 1 H-NMR. As a result, a decrease in the peak derived from the SiO—CH 3 group and a peak derived from the Si—OH group were observed. Confirmed the appearance of.
  • component (b) component organopolysiloxane (hereinafter referred to as “component (b) component organopolysiloxane”) and preparation of solution of organopolysiloxane (b) composition
  • component (b) component organopolysiloxane component organopolysiloxane
  • preparation of solution of organopolysiloxane (b) composition In a 1 L flask, about 30 nm 167 g of water-dispersed silica sol having an average particle size (pH 3.1, solid content of silica fine particles of 20% by mass) and 14 g of acetic acid were charged, and 136 g of methyltrimethoxysilane was added. After stirring for 1 hour, the pH of the composition stabilized at 4.5. This composition was aged at 25 ° C. for 4 days and partially hydrolyzed and condensed. Thus, a solution (PSi-1 concentration: 40% by mass) containing component (b) organopolysiloxan
  • the obtained organopolysiloxane (b) is almost free from monomeric T0 form [R—Si (OH) 3 ] (R is CH 3 ), and the raw material methyltrimethoxysilane is an oligomeric organopolysiloxane. It was confirmed that it was almost completely converted to siloxane.
  • Mn of the obtained (b) organopolysiloxane PSi-1 was 400, Mw was 670, and Mw / Mn was 1.68.
  • a benzophenone-based ultraviolet absorber was added to 100 parts by mass of the organopolysiloxane (b) PSi-1 solution obtained above and aged at 25 ° C. for 24 hours or more.
  • a diluent solvent a mixed solvent composed of 40: 40: 15: 5 (mass ratio) of 1-butanol: isopropanol: methanol: 1-methoxy-2-propanol was used, and the non-volatile component was 25% by mass (150 ° C., 45 Min), a solution of an organopolysiloxane (b) PSi-1 composition having a viscosity of 4.4 mPa ⁇ s was prepared.
  • composition for forming hard coat layer (b) Component organopolysiloxane obtained in [2] above was added to the solution containing component (a) organopolysiloxane MSi-1 obtained in [1] above.
  • composition solution containing the component (b) organopolysiloxane PSi-1 obtained in [2] above was designated as a hard coat layer forming composition HC-2.
  • Example 1 A bisphenol A-based polycarbonate resin plate (Carbo Glass (registered trademark) Polish Clear (trade name, manufactured by Asahi Glass Co., Ltd.)) having a thickness of 3 mm is coated with primer layer forming composition P-1 to a thickness of 4 ⁇ m by dip coating. After being left to stand at 25 ° C. for 20 minutes, it was cured by heating at 120 ° C. for 30 minutes using a hot air circulating dryer (manufactured by Enomoto Kasei Co., Ltd., HISPEC HS250).
  • Carbo Glass (registered trademark) Polish Clear trade name, manufactured by Asahi Glass Co., Ltd.
  • the adhesive layer forming composition Ad-1 was applied by spin coating so as to have a film thickness of 3 ⁇ m, allowed to stand at 25 ° C. for 20 minutes, and then at 120 ° C. for 30 minutes. Cured by heating for minutes.
  • the hard coat layer forming composition HC-1 was applied by spin coating so as to have a film thickness of 3 ⁇ m, allowed to stand at 25 ° C. for 20 minutes, and then heated at 120 ° C. for 1 hour to be cured. It was.
  • a resin substrate with a hard coat film (resin substrate having a hard coat layer) was produced.
  • Example 2 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the adhesive layer forming composition Ad-1 was applied by spin coating so that the film thickness was 1 ⁇ m.
  • Example 3 A resin substrate with a hard coat film was produced in the same manner as in Example 1 except that the adhesive layer forming composition Ad-2 was applied by spin coating so as to have a film thickness of 3 ⁇ m.
  • Example 4 A resin substrate with a hard coat film was produced in the same manner as in Example 3 except that the adhesive layer forming composition Ad-2 was applied so as to have a film thickness of 1 ⁇ m.
  • Example 5 A resin substrate with a hard coat film was produced in the same manner as in Example 1 except that the adhesive layer forming composition Ad-3 was applied by spin coating so that the film thickness was 0.5 ⁇ m.
  • Example 6 A resin substrate with a hard coat film was produced in the same manner as in Example 5 except that the adhesive layer forming composition Ad-3 was applied so as to have a film thickness of 1 ⁇ m.
  • Example 7 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the adhesive layer forming composition Ad-4 was applied by spin coating so that the film thickness became 0.5 ⁇ m.
  • Example 8 A resin substrate with a hard coat film was produced in the same manner as in Example 7 except that the adhesive layer forming composition Ad-4 was applied so as to have a film thickness of 1 ⁇ m.
  • Example 9 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the adhesive layer forming composition Ad-5 was applied by spin coating so that the film thickness became 0.5 ⁇ m.
  • Example 10 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the adhesive layer forming composition Ad-6 was applied by spin coating so that the film thickness became 0.5 ⁇ m.
  • Example 11 The adhesive layer forming composition Ad-3 was applied by spin coating so that the film thickness was 0.5 ⁇ m.
  • the composition for forming a hard coat layer was HC-2. Other than that was carried out similarly to Example 1, and produced the resin substrate with a hard-coat film.
  • Example 12 A 3 mm thick polycarbonate resin plate (Carboglass (registered trademark) polish clear) is coated with the primer layer forming composition P-1 by a dip coating method to a film thickness of 4 ⁇ m and left at 25 ° C. for 20 minutes. Then, it was cured by heating at 120 ° C. for 30 minutes.
  • Carboglass registered trademark
  • the hard coat layer forming composition HC-1 was applied by spin coating so as to have a film thickness of 3 ⁇ m, left at 25 ° C. for 20 minutes, and then at 120 ° C.
  • a resin substrate with a hard coat film was prepared by heating and curing for 1 hour.
  • a primer layer-forming composition P-1 was applied to a polycarbonate resin plate (Carbo Glass (registered trademark) polish clear) with a thickness of 3 mm so as to have a film thickness of 4 ⁇ m by dip coating, and left at 25 ° C. for 20 minutes. Thereafter, it was cured by heating at 120 ° C. for 30 minutes.
  • a polycarbonate resin plate Carbo Glass (registered trademark) polish clear
  • the adhesive layer forming composition Ad-7 was applied by spin coating so as to have a film thickness of 0.5 ⁇ m, allowed to stand at 25 ° C. for 20 minutes, and then 120 ° C. For 30 minutes to cure.
  • the hard coat layer forming composition HC-1 was applied by spin coating so as to have a film thickness of 3 ⁇ m, allowed to stand at 25 ° C. for 20 minutes, and then cured by heating at 120 ° C. for 1 hour, A resin substrate with a hard coat film was prepared.
  • a primer layer-forming composition P-1 was applied to a polycarbonate resin plate (Carbo Glass (registered trademark) polish clear) with a thickness of 3 mm so as to have a film thickness of 4 ⁇ m by dip coating, and left at 25 ° C. for 20 minutes. Thereafter, it was cured by heating at 120 ° C. for 30 minutes.
  • a polycarbonate resin plate Carbo Glass (registered trademark) polish clear
  • the adhesive layer forming composition Ad-8 having no hydrolyzable silyl group was applied on the primer layer thus formed so as to have a film thickness of 0.5 ⁇ m by spin coating, and 25 ° C. For 20 minutes and then heated at 120 ° C. for 30 minutes to cure. Further thereon, the hard coat layer forming composition HC-1 was applied by spin coating so as to have a film thickness of 3 ⁇ m, allowed to stand at 25 ° C. for 20 minutes, and then cured by heating at 120 ° C. for 1 hour, A resin substrate with a hard coat film was prepared.
  • Adhesive layer forming composition Ad-7 was applied as a primer to a 3 mm thick polycarbonate resin plate (Carbograss (registered trademark) polish clear) by a dip coating method to a film thickness of 4 ⁇ m, and 20 ° C. at 25 ° C. After being left for a minute, it was cured by heating at 120 ° C. for 30 minutes.
  • a 3 mm thick polycarbonate resin plate Carbograss (registered trademark) polish clear
  • the hard coat layer forming composition HC-1 was applied by spin coating so as to have a film thickness of 3 ⁇ m, left at 25 ° C. for 20 minutes, and then at 120 ° C. It was cured by heating for 1 hour to prepare a resin substrate with a hard coat film.
  • the following weather resistance test was performed. That is, an accelerated weathering tester using a metal halide lamp as a light source (Daipura Wintes; Daipla Metal Weather KW-R5TP-A) is used for 50 cycles (600 cycles of three conditions of light irradiation, condensation, and darkness). Time) loaded.
  • the light irradiation conditions are such that light is irradiated for 4 hours at an illuminance of 80 mW / cm 2 , a black panel temperature of 63 ° C., and a relative humidity of 80%, and the dew condensation conditions are 98% relative humidity without light irradiation.
  • the black panel temperature is naturally cooled from 63 ° C. to 30 ° C. and held for 4 hours, and the dark conditions are maintained for 4 hours at a black panel temperature of 75 ° C. and a relative humidity of 90% without light irradiation. Is. Further, a shower was performed for 10 seconds before and after the condensation.
  • a composition for forming an adhesive layer mainly composed of a silyl group-containing acrylic polymer having a hydrolyzable silyl group bonded to the side chain is applied.
  • the resin substrate with a hard coat film of Examples 1 to 11 having a dried adhesive layer has a small initial haze (cloudiness value) and good appearance, a haze difference after the Taber test of 10 or less, and scratch resistance. Sex was acceptable. Moreover, the appearance of the hard coat film after the weather resistance test was good, and the weather adhesion was also excellent.
  • Example 13 in which the adhesive layer was constituted by the composition described in Synthesis Example 7 on the primer layer, the UV-absorbing property in which the silyl group-containing acrylic polymer constituting the adhesive layer is an aromatic hydrocarbon group. It is considered that the adhesiveness between the adhesive layer, the hard coat layer and the primer layer is insufficient due to the inclusion of the polymerized unit having a group. As a result, the initial haze was large and the haze difference after the Taber test was large, so that the initial scratch resistance of the hard coat film was insufficient. In addition, cracks and peeling occurred in the hard coat film after the weather resistance test, the appearance judgment after the weather resistance test was “x” and not only was rejected, but also the adhesion was poor.
  • Example 14 in which the adhesive layer was composed of a composition having no hydrolyzable silyl group, since the adhesiveness between the adhesive layer, the hard coat layer and the primer layer was insufficient, the initial haze was large, The haze difference after the Taber test was large, and the initial scratch resistance of the hard coat film was insufficient.
  • Example 15 in which a primer layer was formed from the composition described in Synthesis Example 7 and a hard coat layer was formed thereon, the silyl group-containing acrylic polymer constituting the primer layer was an aromatic hydrocarbon group. It is considered that the adhesion between the hard coat layer and the primer layer is insufficient due to the fact that it contains a polymerization unit having an ultraviolet absorbing group. As a result, the initial haze was large and the haze difference after the Taber test was large, so that the initial scratch resistance of the hard coat film was insufficient. Furthermore, cracks and peeling occurred in the hard coat film after the weather resistance test, and the appearance determination after the weather resistance test was “x”, which was not only rejected, but also the adhesion was poor.
  • the resin substrate with a hard coat film of the present invention can be suitably used as a window glass for vehicles attached to automobiles and various transportation facilities, and a window glass for building materials attached to buildings such as houses and buildings.
  • a window glass for vehicles attached to automobiles and various transportation facilities and a window glass for building materials attached to buildings such as houses and buildings.
  • SYMBOLS 1 Resin substrate with a hard coat film
  • 2 Resin substrate
  • 3 Acrylic primer layer
  • 4 Adhesive layer
  • 5 Silicone hard coat layer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

La présente invention concerne un substrat en résine auquel est fixé un film de revêtement dur, qui présente une structure telle qu'une couche de revêtement dur est disposée sur un substrat en résine par le biais d'une couche primaire, et qui présente une excellente résistance à la rayure et une excellente résistance aux intempéries comprenant des propriétés d'adhérence après un test de résistance aux intempéries accélérées et des propriétés de craquelure après un test de résistance aux intempéries ; et un procédé de production du substrat en résine auquel est fixé un film de revêtement dur. A cet effet, le substrat en résine auquel est fixé un film de revêtement dur comprend : une couche primaire qui contient un polymère acrylique comme composant principal ; une couche de revêtement dur qui contient un produit durci d'un organopolysiloxane comme composant principal ; et une couche adhésive qui est disposée entre la couche primaire et la couche de revêtement dur et qui contient, comme composant principal, un polymère acrylique contenant le groupe silyle qui présente un groupe silyle hydrolysable et/ou un groupe SiOH dans une chaîne latérale et ne contient pas d'unité polymérisable présentant un groupe hydrocarbure aromatique dans une chaîne latérale.
PCT/JP2011/073013 2010-10-05 2011-10-05 Substrat en résine auquel est fixé un film de revêtement dur et son procédé de production WO2012046784A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014043572A (ja) * 2012-08-01 2014-03-13 Sumitomo Chemical Co Ltd シリコーン樹脂組成物
JP2015030165A (ja) * 2013-08-01 2015-02-16 旭硝子株式会社 ハードコート被膜付き樹脂基板の製造方法およびハードコート被膜付き樹脂基板
EP3061586A4 (fr) * 2013-10-25 2016-12-21 Asahi Glass Co Ltd Procédé de production d'un substrat de résine avec film de revêtement dur, et substrat de résine avec film de revêtement dur
KR101746460B1 (ko) * 2015-11-20 2017-06-13 현대자동차주식회사 폴리카보네이트 글레이징용 코팅도료 조성물로 코팅된 도장품
US9840641B2 (en) 2014-01-24 2017-12-12 Sumitomo Chemical Company, Limited Silicone resin liquid composition
WO2020165125A1 (fr) * 2019-02-15 2020-08-20 Covestro Intellectual Property Gmbh & Co. Kg Nouveaux systèmes pour l'application de sous-couche et le collage de revêtements de sol

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03168227A (ja) * 1989-11-28 1991-07-22 Nippon Sheet Glass Co Ltd 被覆ポリカーボネート系樹脂成形物品
JPH08309934A (ja) * 1995-05-22 1996-11-26 Teijin Ltd 表面を保護されたプラスチック成形体及びその製造方法
JP2008201882A (ja) * 2007-02-20 2008-09-04 Kansai Paint Co Ltd 水性プライマー組成物、及びこの組成物を用いた塗装方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03168227A (ja) * 1989-11-28 1991-07-22 Nippon Sheet Glass Co Ltd 被覆ポリカーボネート系樹脂成形物品
JPH08309934A (ja) * 1995-05-22 1996-11-26 Teijin Ltd 表面を保護されたプラスチック成形体及びその製造方法
JP2008201882A (ja) * 2007-02-20 2008-09-04 Kansai Paint Co Ltd 水性プライマー組成物、及びこの組成物を用いた塗装方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014043572A (ja) * 2012-08-01 2014-03-13 Sumitomo Chemical Co Ltd シリコーン樹脂組成物
JP2015030165A (ja) * 2013-08-01 2015-02-16 旭硝子株式会社 ハードコート被膜付き樹脂基板の製造方法およびハードコート被膜付き樹脂基板
EP3061586A4 (fr) * 2013-10-25 2016-12-21 Asahi Glass Co Ltd Procédé de production d'un substrat de résine avec film de revêtement dur, et substrat de résine avec film de revêtement dur
US10357908B2 (en) 2013-10-25 2019-07-23 AGC Inc. Method for manufacturing resin substrate with hard coating film and resin substrate with hard coating film
US9840641B2 (en) 2014-01-24 2017-12-12 Sumitomo Chemical Company, Limited Silicone resin liquid composition
KR101746460B1 (ko) * 2015-11-20 2017-06-13 현대자동차주식회사 폴리카보네이트 글레이징용 코팅도료 조성물로 코팅된 도장품
WO2020165125A1 (fr) * 2019-02-15 2020-08-20 Covestro Intellectual Property Gmbh & Co. Kg Nouveaux systèmes pour l'application de sous-couche et le collage de revêtements de sol

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