JPWO2012046784A1 - Resin substrate with hard coat film and method for producing the same - Google Patents

Abstract

In a structure in which a hard coat layer is provided on a resin substrate via a primer layer, a resin substrate with a hard coat film that has excellent scratch resistance and weather resistance such as weather adhesion and weather cracking, and a method for producing the same are provided. To do. Between the primer layer containing the acrylic polymer as the main component and the hard coat layer containing the cured product of the organopolysiloxane as the main component, having a hydrolyzable silyl group and / or SiOH group in the side chain, and It is a resin substrate with a hard coat film provided with an adhesive layer containing as a main component a silyl group-containing acrylic polymer not containing a polymer unit having an aromatic hydrocarbon group in the side chain.

Description

  The present invention relates to a resin substrate with a hard coat film and a method for producing the same.

  In recent years, as a window material for vehicles such as automobiles and window glass for building materials to be attached to buildings such as houses and buildings, a demand for transparent resin plates has been increasing in place of conventional inorganic glass plates. In particular, in vehicles such as automobiles, it has been proposed to use a transparent resin plate for the window material in order to reduce the weight. In particular, an aromatic polycarbonate-based transparent resin plate is resistant to destruction, transparency, lightness, Due to its excellent ease of processing, its use is being considered as a promising vehicle window material. However, such a transparent resin plate has a problem in terms of scratch resistance and weather resistance when used instead of the inorganic glass plate.

  Therefore, for the purpose of improving the scratch resistance and weather resistance of the transparent resin plate, it is possible to form 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.

  However, in the structure in which a primer layer is provided between the transparent resin plate and the hard coat layer, the adhesion and UV resistance are improved by using the primer layer compared to the treatment of only one hard coat layer. However, there were problems in weather resistance such as generation of cracks after long-term use and deterioration of adhesion. In particular, when placed in an environment where ultraviolet irradiation and high humidity are repeated for a long time, there is a problem in that the adhesion between the primer layer and the hard coat layer is lowered and peeling is likely to occur. Here, 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.

  In order to improve the adhesion to the hard coat layer, Patent Document 1 discloses a primer using a copolymer type 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 by a copolymerized polymer of methyl methacrylate, 3-methacryloxypropyltrimethoxysilane, and a reactive ultraviolet absorber. . Further, Patent Document 3 discloses a primer layer forming composition comprising a vinyl polymer having at least one of a hydrolyzable silyl group and SiOH group and an organic ultraviolet absorbing group in the side chain, and an organopolysiloxane, And the coated article which has the primer layer which coat | covered and hardened this composition is proposed.

  However, in these resin substrates and coated articles with a hard coat layer, the adhesion between the primer layer and the hard coat layer in a high humidity environment is not sufficient, and particularly accelerated weathering resistance under severe UV irradiation and humidity conditions When the test was performed, there was a case where peeling occurred between the primer layer and the hard coat layer.

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. Applying and drying a primer layer forming composition contained as a main component to form the primer layer, and having a hydrolyzable silyl group and / or SiOH group in the side chain on the primer layer And applying 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; On the adhesive layer, a composition for forming a hard coat layer containing the organopolysiloxane as a main component is applied and cured to form the hard coat layer. Characterized in that it comprises the steps of, a.

  In the present specification, the “hard coat film” refers to a multi-layer 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” means a silyl group in which a hydrolyzable group is directly bonded to a silicon atom. Here, the “hydrolyzable group” refers to a group that becomes a hydroxyl group (—OH group) by hydrolysis. Therefore, the term “hydrolyzable silyl group and / or SiOH group” means a silyl group in which a hydrolyzable group is bonded to a silicon atom, including a part of which has been converted into a hydroxyl group (—OH group) by hydrolysis. means. Specific examples of the hydrolyzable group will be described in detail later.

  In the present specification, 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 crack resistance. 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.

It is sectional drawing of the resin substrate with a hard coat film of this invention.

  Embodiments of the present invention will be described below.

  One embodiment of the resin substrate with a hard coat film of the present invention is shown in FIG. 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. An adhesive layer 4 containing, as a main component, a silyl group-containing acrylic polymer that has a hydrolyzable silyl group and / or SiOH group and does not contain a polymer unit having an aromatic hydrocarbon group in the side chain, and 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. Since it is considered that a siloxane bond (—O—Si—O—) is formed by reacting with a group and / or SiOH group, 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.

  Hereinafter, each layer which comprises the resin substrate with a hard coat film of this invention is demonstrated in detail.

(1) Resin Substrate 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.

Among these, polycarbonate resins such as aromatic polycarbonate resins or acrylic resins such as polymethyl methacrylate acrylic resins are preferable, and polycarbonate resins are more preferable. Furthermore, among polycarbonate resins, bisphenol A-based polycarbonate resins are particularly preferable. 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.
The thickness of the resin substrate may be appropriately selected depending on the application. 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.

(2) Primer layer 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.

  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. Preferably, 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. Examples of the monomer having an acrylic group include acrylic acid esters. A methacrylic acid ester is mentioned as a monomer which has a methacryl group.

  In the present specification, the notation “(meth) acryl...” Such as (meth) acrylic acid ester means both “acryl ....” and “methacryl ...”.

  The monomer having a methacryl group is preferably a methacrylic acid alkyl ester having an alkyl group having 6 or less carbon atoms. 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.

  Also preferred are copolymers of a main monomer selected from the group consisting of alkyl methacrylates having an alkyl group with 6 or less carbon atoms and at least one of other acrylic esters and methacrylic esters. Examples of 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. Moreover, 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. Examples of the cycloalkyl group 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. Here, 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.

  Moreover, it is preferable that the glass transition point of this acrylic polymer is 60 to 150 degreeC. 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. In addition, the glass transition point of an acrylic polymer becomes like this. More preferably, it is 70 to 120 degreeC, Most preferably, it is 90 to 110 degreeC.

  Furthermore, 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. 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. In addition, in this specification, 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. In general, 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.

  In addition, such an acrylic polymer is also commercially available. In the present invention, 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. Further, 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. Thereby, since the primer layer absorbs ultraviolet rays and the ultraviolet rays do not reach the resin substrate, yellowing of the resin substrate can be suppressed. As the ultraviolet absorber, it is preferable to use an ultraviolet absorber having an average value of an absorption coefficient of 3.5 g / (mg · cm) to 100 g / (mg · cm) for light in a wavelength region of 350 nm to 380 nm. It is more preferably 0 g / (mg · cm) to 50 g / (mg · cm).

  Here, 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 ε is a value obtained from the following relational expression, Equation 1.

[Equation 1]
E = ε · c · d = log (Io / I)
(E: Absorbance, ε: Absorption coefficient (g / (mg · cm)), c: Absorbing component concentration (mg / g), d: Cell thickness (cm), Io: Incident light intensity, I: After transmission Light intensity)

  As described above, in the relatively long wavelength region of 350 to 380 nm among ultraviolet rays, the absorption coefficient absorbs ultraviolet rays with an average value in the range of 3.5 g / (mg · cm) to 100 g / (mg · cm). It is preferable that 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.
Among the above, 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 average extinction coefficient of the ultraviolet absorber for light in the wavelength region of 350 nm to 380 nm is 3.5 g / (mg · cm) to 100 g / (mg · cm ) Is preferred.

  The primer layer may further contain a light stabilizer and the like. Examples of 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 0.01 to 50 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of a resin component such as an acrylic polymer.

  In the resin substrate with a hard coat film of the present invention, 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 composition for forming a primer layer usually contains a solvent. The solvent is not particularly limited as long as it can dissolve the acrylic polymer for primer stably. Specifically, 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, xylene, gasoline, light oil, and kerosene; acetonitrile, nitromethane, and water. These may use 1 type and may use 2 or more types together.

  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. In addition, it is preferable that content of the non-volatile component (solid content) in the composition for primer layer formation is 0.5-75 mass% with respect to the composition whole quantity, and it is especially 1-60 mass%. 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 spray coating, dip coating, flow coating, die coating, and spin coating. Moreover, although the heating conditions for drying are not specifically limited, It is preferable that it is 5 minutes-3 hours at 50-140 degreeC.

  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. Although there is no particular limitation as long as it is present, the thickness is appropriately adjusted in consideration of the thickness of the adhesive layer and the hard coat layer formed on the primer layer. In the resin substrate with a hard coat film finally obtained, if 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. In addition, 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

  Specifically, the thickness of the primer layer before the adhesive layer and the hard coat layer are formed is preferably 0.1 μm to 10 μm, and particularly preferably 1 μm to 7 μm.

(3) Adhesive layer 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. Alternatively, a silyl group-containing acrylic polymer having a SiOH group is used as a main component.

  Here, 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. A polymer based on the reaction between hydrolyzable silyl groups and / or SiOH groups contained in the side chain of the polymer, or the hard coat layer described later with hydrolyzable silyl groups and / or SiOH groups of the polymer. It is considered that a siloxane bond is formed by a reaction between the hydrolyzable silyl group and / or SiOH group of the organopolysiloxane constituting the component. Therefore, “adhesive layer containing, as a main component, a silyl group-containing acrylic polymer having no hydrolyzable silyl group and / or SiOH group in the side chain and no polymerized unit having an aromatic hydrocarbon group in the side chain. In the expression, the side chain hydrolyzable silyl group and / or SiOH group should be interpreted as including a siloxane bond. Below, the silyl group containing acrylic polymer which comprises an contact bonding layer is demonstrated. In addition, it is preferable that the hydrolyzable silyl group and / or SiOH group is bonded to the hydrocarbon group constituting the side chain of the acrylic polymer via a C—Si bond.

  This silyl group-containing acrylic polymer contains polymerized units having one hydrolyzable silyl group and / or SiOH group in the side chain (hereinafter sometimes referred to as “silyl group-containing polymerized 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. In addition, 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. By having a hydroxyalkyl group in the side chain, the affinity with the hard coat layer is increased, the mixing of the adhesive layer and the hard coat layer is appropriately promoted, and the adhesion is improved.

  Furthermore, this silyl group-containing acrylic polymer does not contain polymerized units 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. When 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.

  First, among the 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.

(3-1) Silyl group-containing acrylic polymer (1)
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.

  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. Alternatively, any monomer having a methacryl group can be used without any particular limitation. In particular, 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. Here, as described above, 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. Group, butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as tert-butoxy group, acyloxy group such as phenoxy group, acetyloxy group, oxime group such as butanoxime group, amino group such as amino group, methylamino group And halogen groups such as a chloro group. Alkoxy groups such as a methoxy group and an ethoxy group are preferred because of easy controllability of hydrolyzability and availability. Examples of the substituent other than the hydrolyzable group 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.

  Examples of the acrylic monomer to which such a hydrolyzable silyl group is bonded include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, and 3-methacrylic acid. Examples include loxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane. Among these, 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.

  Examples of the copolymerizable acrylic monomer (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. (C) The other copolymerizable acrylic monomer may be one type or two or more types. Among these, acrylic acid ester or methacrylic acid ester having a linear alkyl group having 2 to 16 carbon atoms is preferable. Specifically, ethyl methacrylate (EMA), n-butyl methacrylate (BMA), decyl methacrylate (DMA ), Lauryl methacrylate (LMA), cetyl methacrylate (CMA) and the like. In the case of a linear alkyl group, the compatibility with the polymethyl methacrylate, which is the main component of the primer layer, is higher than that of the branched alkyl group, and thus it is suitable as an adhesive layer. Further, the glass transition temperature (Tg) of the polymer can be appropriately controlled by the length of the straight chain.

  In the silyl group-containing acrylic polymer (1) of the present invention, 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 as -98 mol%. Moreover, it is preferable that the content rate of the polymerization unit based on (A) silyl group containing acrylic monomer shall be 0.5-50 mol% of the whole polymerization unit which comprises this silyl group containing acrylic polymer (1). That is, the copolymerization composition in the silyl group-containing acrylic polymer (1) is such 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 polymerization unit 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. Furthermore, when it has a polymerization unit based on (C) another copolymerizable acrylic monomer, the content ratio is 0 to 20 mol% of the entire polymerization unit constituting the silyl group-containing acrylic polymer (1). It is preferable.

  (A) When the content ratio of the polymerized units based on the silyl group-containing acrylic monomer is less than 0.5 mol%, the hydrolyzable silyl group and / or SiOH group contained in the polymerized unit constitutes a hard coat layer described later. The reaction with the terminal group (for example, Si-OX group, where -OX represents a hydroxyl group or an alkoxy group) possessed by the organopolysiloxane is not formed, and adhesion with the hard coat layer by providing an adhesive layer The improvement effect cannot be obtained sufficiently. In addition, when the polymer unit based on (A) the silyl group-containing acrylic monomer exceeds 50 mol%, the polymer unit based on (B) methyl methacrylate (MMA) inevitably becomes less than 50 mol%. And the adhesion becomes poor. Moreover, since unreacted hydrolyzable groups are likely to remain, post-crosslinking with time may occur, and cracks may easily occur.

  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. For 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 is 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).

As an example of the 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.

  In this compositional formula, X and Y each represent a molar ratio of (B) polymerized units based on methyl methacrylate (MMA) and (A) polymerized units based on 3-methacryloxypropyltrimethoxysilane. In the silyl group-containing acrylic polymer that is a binary copolymer, X + Y = 100, and the ratio of X: Y is preferably 50:50 to 98: 2.

  Next, 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.

(3-2) Silyl group-containing acrylic polymer (2)
The silyl group-containing acrylic polymer (2) comprises a polymer unit in which a hydrolyzable silyl group and / or SiOH group is bonded to a side chain via a C-Si bond (silyl group-containing polymer unit), and a hydroxy group in the side chain. It has a polymerized unit having an alkyl group (C—OH group) (hereinafter sometimes referred to as “C—OH group-containing polymerized unit”) and a polymerized unit based on (B) methyl methacrylate (MMA).

  The silyl group-containing polymer unit is obtained, for example, by polymerizing an acrylic monomer (silyl group-containing acrylic monomer) having the hydrolyzable silyl group and / or SiOH group bonded via the (A) C—Si bond. be able to. Further, the C—OH group-containing polymerization 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”). Can be obtained. 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.

  (A) The 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, and 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) the silyl group-containing acrylic monomer, (B) methyl methacrylate (MMA) and (D) the 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.

  In the silyl group-containing acrylic polymer (2) of the present invention, 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 as -98 mol%. Moreover, it is preferable that the content rate of a silyl group containing polymerization unit shall be 0.5-50 mol% of the whole polymerization unit which comprises a silyl group containing acrylic polymer (2).

  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 (however, -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. . Further, if 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.

  From the viewpoint of improving the familiarity with the hard coat layer and further improving the adhesion, 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 to set it as -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 preferable to make it 0-45 mol% of the whole polymerization unit which comprises 2).

  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%.

  Next, an example of the copolymer composition of the silyl group-containing acrylic polymer (2) is shown. As shown in the following composition formula, this silyl group-containing acrylic polymer (2) comprises (A) a polymer unit based on 3-methacryloxypropyltrimethoxysilane, which is a silyl group-containing acrylic monomer, and (B) methacryl. Polymer unit based on methyl acid (MMA), (D) Polymer unit based on 2-hydroxyethyl methacrylate (HEMA) which is acrylic monomer containing C-OH group, and (C) Other copolymerizable acrylic monomer The polymerized unit is based on lauryl methacrylate (LMA) and the polymerized unit is based on n-butyl methacrylate (BMA).

  In the above composition formula, 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). 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 2-hydroxyethyl methacrylate (HEMA) which is an acrylic monomer is preferably 0.5-20. Furthermore, the molar ratios q and r of polymer units based on (C) other copolymerizable acrylic monomers lauryl methacrylate (LMA) and n-butyl methacrylate (BMA) are 0-20 and 0-30, respectively. It is preferable that it is 0-40 in total.

(3-3) Synthesis of silyl group-containing acrylic polymer (2) The silyl group-containing acrylic polymer (2) can be obtained by the first synthesis method or the second synthesis method described below.

(3-3-1) First Synthesis Method A silyl group-containing acrylic polymer (2) comprises (A) a silyl group-containing acrylic monomer, (B) methyl methacrylate (MMA), and (D) C-OH. In a solution containing 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 An initiator for radical polymerization 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.

(3-3-2) 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. In this copolymerization, 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). By adding an initiator for radical polymerization and reacting with heating (40 to 150 ° C., particularly 50 to 120 ° C. for 1 to 10 hours, particularly 3 to 8 hours), the first acrylic polymer (intermediate) is obtained. can get. Here, (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). (D) The C—OH group-containing acrylic monomer has a polymer unit based on the molar ratio of the C—OH group-containing polymer unit in the desired silyl group-containing acrylic polymer (2) finally obtained, It mix | blends so that it may become equal to the sum total with the molar ratio of a group containing polymerization unit.

  Thus, (B) polymer units based on methyl methacrylate (MMA), (D) C—OH group-containing polymer units based on C—OH group-containing acrylic monomers, and (C) other copolymerizable acrylic systems A copolymer having polymerized units based on the monomer (hereinafter sometimes referred to as “first acrylic polymer”) is obtained.

Such a first acrylic polymer is also commercially available. In the present invention, 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 polymer units based on units, 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 Super HZ-L + TSKgel Super HZ 4000 + HZ 3000 + HZ 2500 + HZ 2000, eluent: THF, eluent: R). The polymerization unit and its molar ratio are determined by dissolving in deuterated chloroform and nuclear magnetic resonance analysis ( ¹³ C-NMR, ECA600 manufactured by JEOL Ltd.).

(ii) Synthesis of silyl group-containing acrylic polymer (2) 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. Examples of 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. Examples of such a compound having an isocyanate group and a hydrolyzable silyl group and / or SiOH group (hereinafter sometimes referred to as “silyl group-containing isocyanate”) include 3-isocyanatepropyltriethoxysilane, 3 -Isocyanatopropyltrimethoxysilane and the like.

  By reacting with such a silyl group-containing isocyanate, 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 C—OH group-containing polymer units, the side chain has a hydrolyzable silyl group and a side chain by reacting the isocyanate group of the silyl group-containing isocyanate with the C—OH group of the side chain. / Or SiOH groups are introduced. By appropriately adjusting the molar ratio of the C—OH group-containing polymerization unit contained in the first acrylic polymer and the isocyanate group of the silyl group-containing isocyanate, 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.

  Thus, a silyl group-containing acrylic polymer (2) is obtained by modifying a part of the C—OH group-containing polymer unit of the first acrylic polymer into a silyl group-containing polymer unit. Of the C—OH group-containing polymer units possessed by the first acrylic polymer, 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). 5 to 75 mol%. When the C—OH group-containing polymerization unit contains one C—OH group, the modification rate is the ratio of the group reacted with the isocyanate group among the C—OH groups of the first acrylic polymer. You can also.

A specific example of the synthesis of the silyl group-containing acrylic polymer (2) by the second method is shown by the following reaction formula [Chemical Formula 3].

  In this reaction formula [Chemical Formula 3], methyl methacrylate (MMA), lauryl methacrylate (LMA), n-butyl methacrylate (BMA), and 2-hydroxyethyl methacrylate (HEMA) are converted into 67: 3: 21: 9. By reacting 3-isocyanatopropyltriethoxysilane with the first acrylic polymer (I) obtained by copolymerization at a molar ratio, a part of the C—OH group-containing polymer unit is modified and hydrolyzable. A modified polymer (II), which is a silyl group-containing acrylic polymer (2), is obtained as a polymerization unit in which a silyl group (triethoxysilyl group) is introduced.

  Here, among the C—OH group-containing polymer units of the first acrylic polymer, a hydrolyzable silyl group (triethoxysilyl group) is introduced by modification with the reaction of the C—OH group and the isocyanate group. The sum of the molar ratio n of the polymerized units and the molar ratio m of the polymerized units remaining in the C-OH group-containing polymer unit is the molar ratio of the C-OH group-containing polymer units in the first acrylic polymer. It is 9 (n + m = 9). Then, n / (n + m = 9) is the modification rate of the above-described C—OH group-containing polymer unit.

  In the present invention, 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. When 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. When 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.

  Moreover, it is preferable that these silyl group containing acrylic polymers do not contain the polymerization unit which has an aromatic hydrocarbon group in a 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. When 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.

  In the present invention, 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. In the adhesive layer of the resin substrate with a hard coat film obtained in this way, 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.

  In the production of the resin substrate with a hard coat film of the present invention, the adhesive layer forming composition 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. Specifically, 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. These may use 1 type and may use 2 or more types together.

  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. In addition, it is preferable that content of the non-volatile component (solid content) in the composition for contact bonding layer is 0.5-75 mass% with respect to the composition whole quantity, and it is especially 1-50 mass%. preferable. Moreover, this composition for contact bonding layer formation may further contain additives, such as a leveling agent, an antifoamer, and a viscosity modifier.

  A method for applying the adhesive layer forming composition on the primer layer 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. Moreover, although the heating conditions for drying are not specifically limited, It is preferable that it is 5 minutes-3 hours at 50-140 degreeC.

  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 | limited in particular. In the resin substrate with hard coat film finally obtained, if 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. On the other hand, if 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.

  In the adhesive layer containing the silyl group-containing acrylic polymer (1) as a main component, the thickness of the adhesive layer is preferably 0.1 μm to 10 μm, more preferably 1 μm to 5 μm. In the adhesive layer containing the silyl group-containing acrylic polymer (2) as a main component, the thickness is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 2 μm. This film thickness means the thickness when the film is formed alone on a substrate such as a resin substrate.

(4) Hard coat layer 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.

(4-1) Organopolysiloxane The hard coat layer according to the present invention contains a cured product of an organopolysiloxane as a main component. The organopolysiloxane that forms the cured product may be a curable organopolysiloxane. For example, 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. Among these, 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.

In the curable organopolysiloxane, 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. Thus, 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, and T3 has three oxygen atoms. In this specification and the like, an oxygen atom bonded to another silicon atom is represented by O ^* , and a monovalent functional group that can be bonded to another silicon atom is represented by Z.

Note that 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), and a Q unit. Is a unit having 0 organic groups and O ^* 4 (or 4 O ^* 1 to 3 and 3 to 3 Z groups). The monomer forming the T unit is hereinafter referred to as 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 . However, a represents an integer of 0 to 3, R ′ represents a hydrogen atom or a monovalent organic group, and Z represents a monovalent functional group that can be bonded to a hydroxyl group or another silicon atom. In this chemical formula, a compound with a = 3 is an M monomer, a compound with a = 2 is a D monomer, a compound with a = 1 is a T monomer, and a compound with a = 0 is a Q monomer. In the monomer, the Z group is usually a hydrolyzable group. Further, when 2 or 3 R ′ are present (when a is 2 or 3), the plurality of R ′ may be different. 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 ^* . When 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. When 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 ^* ). In the curable organopolysiloxane, 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. At the time of curing, 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. When the curable organopolysiloxane is cured at a high temperature, a cured product in which almost no hydroxyl groups remain may be obtained.

  When 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. In many cases, 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. When 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.

  In the present invention, among these curable organopolysiloxanes, curable organopolysiloxanes having T units as the main silicon-containing bond units are preferably used. Hereinafter, unless otherwise specified, curable organopolysiloxane is simply referred to as organopolysiloxane. Here, in the present specification, an organopolysiloxane having a T unit as a main constituent unit (hereinafter referred to as “organopolysiloxane (T)” as necessary) refers to an M unit, a D unit, a T unit, and The ratio of the number of T units to the total number of Q units refers to an organopolysiloxane having 50 to 100%. In the present invention, the ratio of the number of T units is more preferably 70 to 100%, particularly preferably an organopolysiloxane. 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.

  That is, in the present invention, among these curable organopolysiloxanes, organopolysiloxanes composed only of T units and Q units, and the ratio of the number thereof is T: Q = 90: 10 to 100: 0. Particularly preferably used.

In addition, 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
(In the formula, 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, and O ^* represents two (Represents an oxygen atom connecting silicon atoms)

  R in the chemical formula is not limited to one type, and T1, T2, and T3 may each include a plurality of types of R. Moreover, -OX in the above chemical formula represents a hydroxyl group or an alkoxy group. -OX may be the same or different between T1 and T2. Two -OX in T2 may be different, for example, one may be a hydroxyl group and the other may be an alkoxy group. Moreover, when both -OX is an alkoxy group, those alkoxy groups may be different alkoxy groups. However, as described later, usually, the two alkoxy groups are the same alkoxy group.

In addition, T unit which does not have the oxygen atom (O ^* ) which couple | bonds two silicon atoms, and has three -OX only is hereafter called 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.

  In the organopolysiloxane (T), two or more different T1, T2, and T3 may be present in each molecule. For example, two or more types of T2 with different R may exist. Such organopolysiloxanes are obtained from a mixture of two or more T monomers. For example, in 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. However, 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 T monomer, T1, and T2 may differ depending on the difference in R even if three -OX in T monomer are the same.

The organopolysiloxane (T) is preferably produced from at least one T monomer represented by R—Si (—OY) ₃ . In this formula, 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 alkyl groups having 1 to 10 carbon atoms, alkenyl groups and alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, or carbon numbers. 7-10 aralkyl groups are preferred. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, octyl group, decyl group, vinyl group, allyl group, cyclohexyl group, phenyl Group, benzyl group, phenethyl group and the like.

  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. As the functional group, a hydroxyl group, mercapto group, carboxyl group, epoxy group, amino group, cyano group and the like are preferable. As the halogen atom-substituted organic group, an alkyl group having a chlorine atom or a fluorine atom such as a chloroalkyl group or a polyfluoroalkyl group is preferable. Examples of 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. In particular, chlorine atom, mercapto group, epoxy group, amino group, acryloyloxy group, methacryloyloxy group, glycidyl group, alkylamino group, N-aminoalkyl-substituted aminoalkyl group and the like are 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.

  Specific examples of the substituted organic group 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. Moreover, the organopolysiloxane obtained by using 1 or more types of T monomer which has a C1-C4 alkyl group as organopolysiloxane (T), and a small amount of other T monomers 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. As the other T monomer, 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.

  Specific examples of the 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. Specific examples of the T monomer having a substituted organic group and the like include the following compounds.

  Vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3 -Acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-a Roh propyltrimethoxysilane, 3-cyano-ethyl trimethoxysilane.

The 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 include ethyltrichlorosilane, phenyltrichlorosilane, 3-glycidoxypropyltrichlorosilane, methyltriacetoxysilane, and ethyltriacetoxysilane.

In the D monomer (a = 2) represented by (R'-) _a Si (-Z) _4-a , two R's may be the same or different. In the case of being the same, an alkyl group having 1 to 4 carbon atoms is preferable. When they are different, it is preferable that one R ′ is an alkyl group having 1 to 4 carbon atoms, and the other R ′ is a substituted organic group substituted with the functional group or the functional group-containing organic group. Moreover, as a Z group, a C1-C4 alkoxy group, an acetoxy group, etc. are preferable.

  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-aminopropylmethyldi Examples include ethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-cyanoethylmethyldimethoxysilane.

In _{(R'-) a Si (-Z)} Q monomer represented by _{4-a (a = 0)} , it may be different from four Z groups, but 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 or 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.

  As the catalyst, an acid catalyst is preferable. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and 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. Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, diacetone alcohol, and 2-butoxyethanol. It is done. The reaction temperature can be reacted at room temperature when a catalyst is present. Usually, an appropriate temperature is employed 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 T2 is generated from T2. Condensation reaction in which at least one hydrolyzable group is converted to a hydroxyl group from T0 to T1, a condensation reaction in which at least one of two —OX is a hydroxyl group, T1 to T2 is generated, or T2 in which —OX is a hydroxyl group It is considered that 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. When the reaction conditions are relatively mild, the movement of the abundance peak is considered to proceed relatively orderly. On the other hand, when the reaction conditions are relatively severe, the reaction proceeds randomly and the distribution of the abundance of each unit becomes flat, and the abundance of T0 and T1 tends to be larger than the abundance of T2 and T3. .

  As will be described later, among the organopolysiloxanes (T) used in the present invention, 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 condensation reaction varies depending on R, and when R is different, the reactivity of the hydroxyl group also varies. Usually, the smaller R is (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.

  Furthermore, 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. Therefore, 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. When the reactivity of the hydrolyzable group is sufficiently high, an organopolysiloxane having a high hydroxyl group ratio can be obtained from an organopolysiloxane having a high hydrolyzable group ratio without much progress of the condensation reaction.

  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 | cured material which used the seed or more together as a main component. In addition, in the resin substrate with a hard coat film of the present invention, in order to form a hard coat layer, 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).

(Organopolysiloxane (a))
The organopolysiloxane (a) contains each unit of T1 to T3 at a ratio of T1: T2: T3 = 0 to 5:15 to 40:55 to 85 and T3 / T2 = 1.5 to 4.0. . Further, regarding the OX group in the organopolysiloxane (a), the ratio of the number (A) that is an alkoxy group to the number (B) that is a hydroxyl group, and (B) / (A) is 12 in terms of molecular average. 0.0 or more. And the weight average molecular weight of organopolysiloxane (a) is 800-8,000. The organopolysiloxane (a) does not substantially contain T0 which is a T monomer.

  Regarding the ratio of T1, T2 and T3 constituting the organopolysiloxane (a), in addition to the above conditions, (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. Moreover, about T3 / T2, a preferable range is 2.0-4.0.

  By making the ratio of T1, T2 and T3 constituting the organopolysiloxane (a) in such a range with the average composition of each molecule, the organopolysiloxane (a) and the organopolysiloxane (b) described later can be obtained. When combined with 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). When 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. In addition, 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. The higher the proportion of hydroxyl groups, the better. (B) / (A) in the organopolysiloxane (a) is 12.0 or more, preferably 16.0 or more. Note that (A) may be zero.

  When the value of (B) / (A) is less than 12.0, the proportion of hydroxyl groups is too small compared to the alkoxy groups, and the effect of promoting the curing reaction cannot be obtained, and scratch resistance is caused by the influence of the alkoxy groups. This may lead to a decrease in the thickness and cause post-curing to cause microcracks. That is, when the value of (B) / (A) is less than 12.0, a three-dimensional cross-linked structure formed by a curing reaction of organopolysiloxane (a) and organopolysiloxane (b) when forming a hard coat layer Due to the fact that a part of the organopolysiloxane (a) is not incorporated into the (network) and bleed-out is likely to occur, the crosslinking density is reduced, wear resistance cannot be obtained, and curing is not sufficiently advanced. The problem of becoming.

  The weight average molecular weight of the organopolysiloxane (a) is 800 to 8,000, preferably 1,000 to 6,000. When the weight average molecular weight of the organopolysiloxane (a) is in this range, the hard coat layer for forming the hard coat layer according to the present invention by combining the organopolysiloxane (a) and the organopolysiloxane (b). When used in the forming composition, the scratch resistance and weather resistance of the resulting hard coat layer can be sufficiently improved.

  In the present invention, in order to obtain 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 mass% or more in 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.

  As a method for producing the organopolysiloxane (a), as described above, hydrolysis condensation reaction of T monomer or the like is performed in a solvent in the presence of an acid catalyst. Here, the water required for hydrolysis is usually 1 to 10 mol, preferably 1.5 to 7 mol, and more preferably 3 to 5 mol with respect to 1 mol of the monomer. When the monomer is hydrolyzed and condensed, it can also be carried out in a reaction system in which colloidal silica (described later) is present. When water-dispersed colloidal silica is used as the colloidal silica, water is supplied from this dispersion. Is done. 0.1-50 mass parts is preferable with respect to 100 mass parts of monomers, and, as for the usage-amount of an acid catalyst, 1-20 mass parts is especially preferable. As 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.

  Usually, the reaction temperature is 20 to 40 ° C., and the reaction time is 1 hour to several days. Although 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 organopolysiloxanes. 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.

Examples of commercially available organopolysiloxane that can be used as a raw material for the organopolysiloxane (a) include the following organopolysiloxanes, which are partially hydrolyzed condensates of methyltrimethoxysilane. In addition, the notation of “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).

Methyl silicone resin KR-220L (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); T0: T1: T2: T3 = ND: ND: 28:72, Si—OH / SiO—CH ₃ = 11.7, weight average molecular weight Mw = 4720, number average molecular weight Mn = 1,200, Mw / Mn = 3.93.
Methyl silicone resin KR-500 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); T0: T1: T2: T3 = ND: 15: 58: 27, the peak derived from the Si—OH group was not confirmed by FT-IR, Only substantially SiO—CH ₃ exists. Mw = 1,240, Mn = 700, Mw / Mn = 1.77.

  When the organopolysiloxane (a) is produced from the commercially available organopolysiloxane as described above, it is preferable to mainly hydrolyze the alkoxy group of the commercially available organopolysiloxane in the presence of an acid catalyst. For example, after adding 0 to 10 times amount (mass) of a solvent to commercially available organopolysiloxane and stirring well, an acid aqueous solution of about 0.1 to 70% by mass is added to 15 to 80 ° C., preferably 20 Examples thereof include a method of 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))
The 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). An organopolysiloxane having a weight average molecular weight 1/10 to 1 / 1.5 times Mw. The organopolysiloxane (b) is an organopolysiloxane having a weight average molecular weight smaller than that of 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). When the weight average molecular weight of the organopolysiloxane (b) exceeds 1 / 1.5 times the weight average molecular weight of the organopolysiloxane (a), in other words, 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. When 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). ) Exceeding 10 times the weight average molecular weight, the hard coat layer obtained has low scratch resistance, and a hard coat layer having sufficient scratch resistance cannot be obtained.

  More preferable organopolysiloxane (b) is that each silicon-containing bond unit represented by T0, T1, T2 and T3 is in the ratio of the number of these units, T0: T1: T2: T3 = 0 to 5: 0. It is an organopolysiloxane in the range of 50: 5-70: 10-90. 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. In the 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. In the organopolysiloxane (b), when the ratio of T3 becomes higher than necessary, a hard coat layer forming composition containing the organopolysiloxane (b) and the organopolysiloxane (a) is used to form a hard coat layer. At the time of thermosetting, 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. In addition, 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).

  Here, in the composition for forming a hard coat layer for forming the hard coat layer according to the present invention described below, 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. In the composition for forming a hard coat layer for forming a hard coat layer according to the present invention, if both of them are contained in such a proportion, the organopolysiloxane three-dimensional crosslinked structure formed by the curing reaction becomes an organopolysiloxane. (B) 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.

(4-2) 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 60-95 mass%. In the present specification, 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. For example, in order to further improve the scratch resistance of the hard coat layer of the resin substrate with a hard coat film of the present invention, 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. In order to mix | blend a silica fine particle with the composition for hard-coat layer formation, specifically, it is preferable to mix | blend colloidal silica. Colloidal silica refers to silica fine particles dispersed in water or an organic solvent such as methanol, ethanol, isobutanol, or propylene glycol monomethyl ether.

  Silica fine particles can also be added to the raw material monomer in the process of producing the organopolysiloxane. By producing organopolysiloxane in a reaction system containing colloidal silica, an organopolysiloxane containing silica fine particles can be obtained. For example, 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. Using the organopolysiloxane thus obtained, 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 composition for forming a hard coat layer according to the present invention preferably has 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. Furthermore, 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. Furthermore, it is particularly preferable to use colloidal silica dispersed in an acidic aqueous solution. Further, the colloidal silica may contain inorganic fine particles other than silica fine particles such as alumina sol, titania sol, and ceria sol.

  As content of the silica fine particle in the composition for hard-coat layer formation used for this invention, the quantity used as 1-50 mass% with respect to the composition (nonvolatile component) whole quantity except a solvent is preferable, and it is 5-40 mass%. Is more preferred. If 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. In addition, 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. Moreover, 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 composition for forming a hard coat layer 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 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. When the content of the curing catalyst is less than 0.01 parts by mass, it is difficult to obtain a sufficient curing rate. When 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.

  Moreover, it is preferable that the composition for hard-coat layer formation used for this invention contains a ultraviolet absorber further in order to suppress the yellowing of a resin substrate. As UV absorbers, 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.

  In normal use, 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 structure and weight average molecular weight of the acrylic polymer, the type of organopolysiloxane contained in the composition for forming a hard coat layer, the thickness of the primer layer, the thickness of the adhesive layer, the thickness of the hard coat layer finally obtained, Depending on the coating method of the composition for forming a hard coat layer, the drying and curing method of the composition for forming a hard coat layer, etc., the preferred pH range is generally from 3.5 to 4.5.

  Examples of the pH adjustment method include addition of an acid and adjustment of the content of the curing catalyst. Examples of 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 Examples thereof include organic acids such as sulfonic acid, among which acetic acid or hydrochloric acid is preferable.

  When the above organopolysiloxane (a) is used as the organopolysiloxane in the composition for forming the hard coat layer, 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 an organopolysiloxane that is an essential component and various additives that are 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. For this purpose, the solvent contains at least 20% by mass, preferably 50% by mass or more of alcohol. .

  Examples of the alcohol used in such a solvent 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. Among these, 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. Specifically, 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. In addition, when water in water-dispersed colloidal silica does not participate in the hydrolysis reaction, and when colloidal silica in an organic solvent dispersion is used, the dispersed organic solvent is also included.

  Furthermore, in the composition for forming a hard coat layer used in the present invention, as 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. It is more preferable that it is 150-2,000 mass parts.

(4-3) Formation of Hard Coat Layer 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 onto 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 usual 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 Examples of the solvent drying conditions 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. However, for example, when an organopolysiloxane having a methyl group as a monovalent organic group is used, if the temperature during heat curing is 250 ° C. or higher, the methyl group is eliminated by thermal decomposition, which is not preferable. Accordingly, 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, and particularly preferably 30 minutes to 2 hours.

  The film thickness (film thickness before curing) 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 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 10 μm 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.

  When 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 too small, it is difficult to ensure sufficient scratch resistance. On the other hand, if the thickness of the hard coat layer is too large, cracks and peeling may occur easily. Therefore, in order to suppress the occurrence of cracks and peeling while ensuring sufficient scratch resistance, the film thickness of the hard coat layer is preferably 1 μm or more and 20 μm or less.

In the resin substrate with a hard coat film of the present invention, in order to further improve scratch resistance and film strength, 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. As 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.

[Method for producing resin substrate with hard coat film of the present invention]
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).
(I) Step of forming a primer layer by applying and drying a primer layer forming composition containing the acrylic polymer as a main component on at least one surface of a resin substrate (II) obtained in the above step Step (III) for forming an adhesive layer by applying and drying the adhesive layer-forming composition containing the silyl group-containing acrylic polymer as a main component on the primer layer (III) The adhesive layer obtained in the above step A process for forming a hard coat layer by applying and curing a composition for forming a hard coat layer containing the organopolysiloxane as a main component thereon

  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 Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. Examples 1 to 11 are examples, and examples 12 to 15 are comparative examples.

<Preparation of primer layer forming composition>
Polymethyl methacrylate (PMMA) (number average molecular weight Mn = 120,000, weight average molecular weight Mw = 340,000, dispersity Mw / Mn = 2.8, oxidation 0 mgKOH / g, glass transition temperature 105 ° C.) and UV absorption The agent dibenzoresorcinol (manufactured by Clariant, DBR, extinction coefficient ε (350-380) ave: 5.5) was blended with 10 parts by weight of DBR with respect to 100 parts by weight of PMMA. This was dissolved in a solvent consisting of 1-methoxy-2-propanol: acetone alcohol = 85: 15 (mass ratio) and adjusted so that the non-volatile content was 10% by mass, and the primer layer forming composition P-1 Got.

  In addition, 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.

<Preparation of composition for forming adhesive layer>
A composition for forming an adhesive layer was prepared by the method shown below. In addition, Mw of the obtained resin etc. was calculated | required by the gel permeation chromatography similar to the above.

(Synthesis Example 1)
In a 0.5 liter flask equipped with a stirrer, a condenser and a thermometer, 90 g of methyl methacrylate (MMA), 25 g of 3-methacryloxypropyltrimethoxysilane (MPTM), and 200 g of diacetone alcohol were mixed in a nitrogen stream. Stir in and heat to 80 ° C. Thereafter, 0.7 g of 2,2′-azobis (isobutyronitrile) was added as a polymerization initiator and stirred at 80 to 90 ° C. for 3 hours to copolymerize MMA and MPTM. The molar ratio of MMA to MPTM was 9: 1. The solution thus obtained 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-1 containing a silyl group-containing acrylic polymer. Mw of the obtained silyl group-containing acrylic polymer was 11,400.

(Synthesis Example 2)
In a 0.5 liter flask equipped with a stirrer, a condenser and a thermometer, 80 g of methyl methacrylate (MMA), 50 g of 3-methacryloxypropyltrimethoxysilane (MPTM), and 200 g of diacetone alcohol were mixed in a nitrogen stream. Stir in and heat to 80 ° C. Thereafter, 0.7 g of 2,2′-azobis (isobutyronitrile) was added as a polymerization initiator and stirred at 80 to 90 ° C. for 3 hours to copolymerize MMA and MPTM. The molar ratio of MMA to MPTM was 8: 2. The solution thus obtained 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-2 containing a silyl group-containing acrylic polymer. Mw of the obtained silyl group-containing acrylic polymer was 68,000.

(Synthesis Example 3)
Acrylic polymer JR4811 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymerized units based on methyl methacrylate (MMA), polymerized units based on lauryl methacrylate (LMA), polymerized units based on n-butyl methacrylate (BMA) and 2-hydroxyethyl methacrylate 125 g of a toluene solution (non-volatile content: 22% by mass) having a molar ratio with a polymerization unit based on (HEMA) of 67: 3: 21: 9, Mw 16,000) was provided with a stirrer, a condenser and a thermometer. The flask was placed in a liter flask under a nitrogen stream, and 4 g of 3-isocyanatopropyltriethoxysilane (IPTE) and 0.14 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a catalyst were added and reacted at 80 ° C. for 3 hours. The reaction solution was put into hexane and reprecipitation purification was performed. From the NMR measurement results of the purified product, it was found that 25% of the polymerized units based on 2-hydroxyethyl methacrylate (HEMA) were modified to polymerized units having a triethoxysilyl group. That is, in the modified polymer (II) obtained by the reaction formula [Chemical Formula 3], it was found that n was 2.25, m was 6.75, and the modification rate was 25%.

  The obtained purified product is dissolved in a solvent consisting of 1-methoxy-2-propanol: diacetone alcohol = 85: 15 (mass ratio), and adjusted so that the nonvolatile content becomes 10% by mass, for forming an adhesive layer. It was set as composition Ad-3.

(Synthesis Example 4)
A 0.5 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 125 g of a toluene solution of acrylic polymer JR4811 (nonvolatile content 22% by mass) under a nitrogen stream, and 3-isocyanatopropyltriethoxysilane was added thereto. (IPTE) 12 g and 0.02 g of dibutyltin dilaurate as a catalyst were added and reacted at 80 ° C. for 3 hours. The reaction solution was put into hexane and reprecipitation purification was performed. From the NMR measurement results of the purified product, it was found that 50% of the polymerized units based on 2-hydroxyethyl methacrylate (HEMA) were modified to polymerized units having a triethoxysilyl group. That is, it was found that in the modified polymer (II) obtained by the reaction formula [Chemical Formula 3], n and m were both 4.5 and the modification rate was 50%.

  Next, the purified product is dissolved in a solvent of 1-methoxy-2-propanol: diacetone alcohol = 85: 15 (mass ratio) and adjusted so that the nonvolatile content is 10% by mass. It was set as Ad-4.

(Synthesis Example 5)
In a 0.5 liter flask equipped with a stirrer, a condenser and a thermometer, under a nitrogen stream, 101 g of methyl methacrylate (MMA), 12 g of lauryl methacrylate (LMA), 45 g of n-butyl methacrylate (BMA), 2-hydroxyethyl methacrylate A mixture of 13 g of (HEMA), 9 g of 3-methacrylooxypropyltrimethoxysilane (MPTM), and 268 g of diacetone alcohol was added and heated to 80 ° C. Further, 0.9 g of 2,2′-azobis (isobutyronitrile) was added as a polymerization initiator and stirred at 80 to 90 ° C. for 3 hours to copolymerize MMA, LMA, BMA, HEMA and MPTM. . In addition, the molar ratio of each monomer component was MMA: LMA: BMA: HEMA: MPTM = 67: 3: 21: 6.7: 2.3.

  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.

(Synthesis Example 6)
In a 0.5 liter flask equipped with a stirrer, a condenser and a thermometer, under a nitrogen stream, 105 g of methyl methacrylate (MMA), 45 g of n-butyl methacrylate (BMA), 13 g of 2-hydroxyethyl methacrylate (HEMA), 3- A mixture of 9 g of methacryloxypropyltrimethoxysilane (MPTM) and 257 g of diacetone alcohol was added and heated to 80 ° C. Furthermore, 0.9 g of 2,2′-azobis (isobutyronitrile) was added as a polymerization initiator and stirred at 80 to 90 ° C. for 3 hours to copolymerize MMA, BMA, HEMA and MPTM. The molar ratio of each monomer component was MMA: BMA: HEMA: MPTM = 70: 21: 6.7: 2.3.

  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-6 containing a silyl group-containing acrylic polymer. Mw of the obtained silyl group-containing acrylic polymer was 82,000.

(Synthesis Example 7)
The following synthesis was performed with reference to Synthesis Example 1 of Patent Document 3. 2- [2′-hydroxy-5 ′-(2-methacryloxyethyl) phenyl] -2H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) 22 g, 3-methacryloxypropyltrimethoxysilane (MPTM) 25 g, 70 g of methyl methacrylate (MMA), 6 g of glycidyl methacrylate (GMA), and 96 g of diacetone alcohol were mixed to obtain a monomer mixed solution.

  Further, 0.6 g of 2,2′-azobis (isobutyronitrile) was dissolved in 49 g of diacetone alcohol to obtain a polymerization initiator solution.

  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. Here, 66 g of the monomer mixed solution and 15 g of the polymerization initiator solution prepared in advance were sequentially added. After reacting at 80 ° C. for 30 minutes, the remaining monomer mixed solution and the remaining polymerization initiator solution were simultaneously added dropwise at 80 to 90 ° C. over 1.5 hours. Furthermore, it stirred at 80-90 degreeC 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.

(Synthesis Example 8)
Acrylic polymer JR4811 is dissolved in a solvent consisting of 1-methoxy-2-propanol: diacetone alcohol = 85: 15 (mass ratio), and adjusted so that the nonvolatile content is 10% by mass, thereby forming an adhesive layer forming composition. It was set as thing Ad-8.

<Preparation of composition for forming hard coat layer>
A composition for forming a hard coat layer was prepared by the method shown below. The organopolysiloxane was analyzed by the method shown below.

(1) Number of silicon atom-bonded hydroxyl groups (B) / Number of silicon atom-bonded alkoxy groups (A)
Since the organopolysiloxane used in Examples and Comparative Examples had only a silicon atom-bonded methoxy group (SiO—CH ₃ ) as a silicon atom-bonded alkoxy group, the following (B) / (A) The ratio of Si—OH / SiO—CH ₃ obtained by the above method was used. That is, using an infrared absorption analyzer (FT-IR, manufactured by Thermo Fisher Scientific, model: Avatar / Nicolet FT-IR360), absorption derived from Si—OH in the vicinity of 900 cm ⁻¹ and 2860 cm ^−1. The ratio of the number of Si—OH / SiO—CH ₃ was determined from the area ratio with the absorption derived from nearby SiO—CH ₃ .

(2) Analysis of bonding state of silicon atom in organopolysiloxane Bonding state of silicon atom in organopolysiloxane, specifically, the abundance ratio of T0 to T3 is determined by a nuclear magnetic resonance analyzer ( ²⁹ Si-NMR: manufactured by JEOL Ltd., ECP400) ^was used to determined from the peak area ratio of 29 Si-NMR. The measurement conditions are 10 mmφ sample tube made of polytetrafluoroethylene (PTFE), proton decoupling, pulse width 45 °, waiting time 15 sec, relaxation reagent: Cr (acac) ₃ 0.1 mass%, external standard sample: tetra Methylsilane. The chemical shifts of ²⁹ Si-NMR derived from each structure are as follows.
(T0-T3)
T0: -40 to -41 ppm
T1: -49 to -50 ppm
T2: -57 to -59 ppm
T3: -66 to -70 ppm

(3) Number average molecular weight Mn, weight average molecular weight Mw, and dispersity Mw / Mn
It was determined by gel permeation chromatography (GPC, Waters 2695 manufactured by Waters, RI detection, column: Styragel guard column + HR1 + HR4 + HR5E, eluent: chloroform).

[1] Synthesis of organopolysiloxane (a) (hereinafter referred to as “(a) component organopolysiloxane” if necessary, and preparation of solution containing organopolysiloxane (a)) -Based silicone resin KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd., Si-OH group-derived peak is not confirmed by FT-IR, and is substantially only SiO-CH _3. The abundance ratio of each T unit is T0: T1: (T2: T3 = ND: 15: 58: 27, Mn = 700, Mw = 1240, Mw / Mn = 1.77) 10 g of 1-butanol was added to 10 g and stirred well, 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 mass%) containing (a) component organopolysiloxane MSi-1.

When the obtained MSi-1 was compared with KR-500 as a raw material by FT-IR and ¹ H-NMR, the decrease in the peak derived from the SiO—CH ₃ group and the peak derived from the Si—OH group were observed. Confirmed the appearance of. The ratio of Si—OH / SiO—CH ₃ of MSi-1 obtained from the peak area ratio of FT-IR was 41.0. MSi-1 is composed of T units, and the abundance ratio of each T unit determined from ²⁹ Si-NMR chemical shift was T0: T1: T2: T3 = ND: 1.1: 30.1: 68.8. It was. Moreover, Mn of MSi-1 was 520, Mw was 1150, and Mw / Mn was 2.22.

[2] Synthesis of organopolysiloxane (b) (hereinafter referred to as “component (b) component organopolysiloxane”) and 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) organopolysiloxane PSi-1 was obtained.

The obtained (b) organopolysiloxane PSi-1 has a bond structure mainly composed of T units, and the abundance ratio of each T unit determined from ²⁹ Si-NMR chemical shift is T0: T1: T2: T3. = ND: 2:54:44. The obtained organopolysiloxane (b) is almost free of 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.

  Next, 4 parts by mass of a benzophenone-based UV 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. As a diluting solvent, a mixed solvent composed of 40: 40: 15: 5 (mass ratio) of 1-butanol: isopropanol: methanol: 1-methoxy-2-propanol was used, and a non-volatile component was 25% by mass (150 ° C., 45 Min), a solution of the organopolysiloxane (b) PSi-1 composition having a viscosity of 4.4 mPa · s was prepared.

[3] Preparation of composition for forming hard coat layer (b) Component organopolysiloxane obtained in [2] above in the solution containing component (a) component organopolysiloxane MSi-1 obtained in [1] above A composition solution containing PSi-1 was blended with MSi-1: PSi-1 = 80: 20 (mass ratio) and mixed well to obtain a hard coat layer forming composition HC-1.

  The composition solution containing the component (b) organopolysiloxane PSi-1 obtained in the above [2] was designated as a hard coat layer forming composition HC-2.

[4] Production of Resin Substrate with Hard Coat Coating Using the primer layer forming composition, the adhesive layer forming composition and the hard coat layer forming composition obtained above, Examples 1 to 15 resin substrates with a hard coat film were prepared. In addition, the film thickness of the following primer layers, adhesive layers, and hard coat layers is the thickness of each layer formed alone on the polycarbonate plate, and an interference film thickness measuring device (Spectra Corp Corp., Solid Lambda Thickness) is used. Measured. At this time, the refractive index used was a value of primer layer n = 1.56, adhesive layer n = 1.50, and hard coat layer n = 1.46. That is, when the film was formed alone on the polycarbonate plate, the film formation conditions were set so that the film thickness was the value, and each layer was formed under the conditions.

(Example 1)
A bisphenol A 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 the primer layer forming composition P-1 by a dip coating method to a film thickness of 4 μm. 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).

  Next, on the primer layer thus formed, the adhesive layer forming composition Ad-1 was applied by spin coating so as to have a film thickness of 3 μm, allowed to stand at 25 ° C. for 20 minutes, and then at 120 ° C. for 30 minutes. Cured by heating for minutes. Further thereon, the hard coat layer forming composition HC-1 was applied by spin coating so as to have a film thickness of 3 μm, allowed to stand at 25 ° C. for 20 minutes, and then heated at 120 ° C. for 1 hour to be cured. It was. Thus, 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 μm.

(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 that the film thickness was 3 μm.

(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 μm.

(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 became 0.5 μm.

(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 μm.

(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 was 0.5 μm.

(Example 8)
A resin substrate with a hard coat film was prepared 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 μm.

(Example 9)
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-5 was applied by spin coating so that the film thickness became 0.5 μm.

(Example 10)
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-6 was applied by spin coating so that the film thickness became 0.5 μm.

(Example 11)
The adhesive layer forming composition Ad-3 was applied by spin coating so that the film thickness became 0.5 μm. 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 μm, and left at 25 ° C. for 20 minutes. Then, it was cured by heating at 120 ° C. for 30 minutes.

  Next, on the primer layer thus formed, the hard coat layer forming composition HC-1 was applied by spin coating so as to have a film thickness of 3 μm, 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.

(Example 13)
A primer layer forming composition P-1 was applied to a 3 mm thick polycarbonate resin plate (Carbograss (registered trademark) polish clear) to a thickness of 4 μm by dip coating, and left at 25 ° C. for 20 minutes. Thereafter, it was cured by heating at 120 ° C. for 30 minutes.

  Next, on the primer layer thus formed, the adhesive layer forming composition Ad-7 was applied by spin coating so as to have a film thickness of 0.5 μm, left at 25 ° C. for 20 minutes, and then 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 μm, left at 25 ° C. for 20 minutes, and then heated and cured at 120 ° C. for 1 hour, A resin substrate with a hard coat film was prepared.

(Example 14)
A primer layer forming composition P-1 was applied to a 3 mm thick polycarbonate resin plate (Carbograss (registered trademark) polish clear) to a thickness of 4 μm by dip coating, and left at 25 ° C. for 20 minutes. Thereafter, it was cured by heating at 120 ° C. for 30 minutes.

  Next, 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 μm 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 μm, left at 25 ° C. for 20 minutes, and then heated and cured at 120 ° C. for 1 hour, A resin substrate with a hard coat film was prepared.

(Example 15)
An adhesive layer forming composition Ad-7 was applied as a primer to a 3 mm thick polycarbonate resin plate (Carboglass (registered trademark) polish clear) by a dip coating method so as to have a film thickness of 4 μm. After being left for a minute, it was cured by heating at 120 ° C. for 30 minutes.

  Next, on the primer layer thus formed, the hard coat layer forming composition HC-1 was applied by spin coating so as to have a film thickness of 3 μm, 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.

[5] Evaluation of Resin Substrate with Hard Coat Coating The following items were evaluated for the resin substrates with hard coat coating obtained in Examples 1 to 11 and Examples 12 to 15 of [4] above. Table 1 shows the results of measurement / evaluation of initial appearance, adhesion, scratch resistance, appearance after weathering test (weathering crack resistance), and weathering adhesion, and the types of adhesive layer forming compositions and hard coats. It shows with the film thickness of each layer which comprises a film.

<1> Initial evaluation <1-1> Initial appearance The appearance of the initial hard coat film was visually observed, and the presence or absence of abnormality was determined according to the following criteria.
○: No abnormality ×: Hard coat film has cracks or peeling

<1-2> Initial scratch resistance Based on JIS K7105 (6.4), haze (cloudiness value) was measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd., model: HGM-2). In addition, in accordance with JIS K5600 (5.9), a wear wheel CALIBRASE (registered trademark) CS-10F (manufactured by TABER) is attached to a Taber abrasion tester (manufactured by Toyo Seiki Seisakusho, model: ROTARY ABRASION TESTER), The haze (haze value) after 500 rotations under a load of 500 g was measured, and the haze (haze value) difference ΔH ₅₀₀ before and after the test was defined as scratch resistance. As a criterion for determination of scratch resistance, if ΔH ₅₀₀ ≦ + 10, it is determined to be acceptable.

<1-3> Initial adhesion In accordance with JIS K5600 (5.6), using a razor blade, make 100 grids by making 11 vertical and horizontal cuts at 1 mm intervals in the hard coat film. Then, after a cellotape (registered trademark) (manufactured by Nichiban Co., Ltd., CT24) was adhered well, a peel test was performed. The number of squares remaining without peeling off the hard coat film was taken as X, and the initial adhesion was indicated by X / 100.

<2> Weather resistance test 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. Here, 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.

<2-1> Weathering crack resistance The appearance of the hard coat film after the weather resistance test (50 cycles, 600 hours) was visually observed, and the presence or absence of abnormality was determined according to the following criteria.
○: No abnormality ×: Hard coat film has cracks or peeling

<2-2> Weather resistance adhesion In accordance with JIS K5600 (5.6), 100 hardboards with a razor blade on the hard coat film after the weather resistance test are cut at 11 mm intervals in the vertical and horizontal directions. Eyes were prepared, and after cellotape (registered trademark) (manufactured by Nichiban Co., Ltd., CT24) was adhered well, a peel test was performed. The number of squares remaining without peeling off the hard coat film was taken as X, and the weather resistance adhesion was indicated by X / 100.

  As can be seen from Table 1, between the primer layer and the hard coat layer, 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.

  On the other hand, in the resin substrate with a hard coat film of Example 12 that does not have an adhesive layer between the primer layer and the hard coat layer, initially, the haze is small, the appearance is good, and the scratch resistance is also acceptable. However, after the weather resistance test, cracks and peeling occurred in the hard coat film, and the adhesion was poor.

  Further, in 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.

  Furthermore, in 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.

  Furthermore, in 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.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2010-225573 filed on October 5, 2010 are cited herein as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 ... Resin substrate with a hard coat film, 2 ... Resin substrate, 3 ... Acrylic primer layer, 4 ... Adhesive layer, 5 ... Silicone hard coat layer.

Claims (12)

On at least one surface of the resin substrate,
A primer layer containing an acrylic polymer as a main component;
An adhesive layer containing, as a main component, a silyl group-containing acrylic polymer having a hydrolyzable silyl group and / or SiOH group in the side chain and not containing a polymer unit having an aromatic hydrocarbon group in the side chain;
A hard coat layer containing a cured product of organopolysiloxane as a main component,
It has in order from the said resin substrate side, The resin substrate with a hard-coat film characterized by the above-mentioned.   The silyl group-containing acrylic polymer contains polymerized units based on methyl methacrylate, and the content ratio is 50 to 98 mol% of the entire polymerized units constituting the silyl group-containing acrylic polymer. A resin substrate with a hard coat film as described in 1.   The silyl group-containing acrylic polymer has a polymer unit having the hydrolyzable silyl group and / or SiOH group in the side chain, the hydrolyzable silyl group and / or SiOH group in the side chain, and an aromatic group. The hard coat film according to claim 1 or 2, which is contained in a proportion of 0.5 to 50 mol% of the entire polymerized units constituting the silyl group-containing acrylic polymer not containing polymerized units having a hydrocarbon group in the side chain. With resin substrate.   The resin substrate with a hard coat film according to any one of claims 1 to 3, wherein the silyl group-containing acrylic polymer further has a hydroxyalkyl group in a side chain.   The silyl group-containing acrylic polymer contains polymerized units having the hydroxyalkyl group in the side chain, and the content ratio of the polymerized units is 0.5 to 0.5 of the entire polymerized units constituting the silyl group-containing acrylic polymer. The resin substrate with a hard coat film according to claim 4, which is 30 mol%.   The silyl group-containing acrylic polymer has a polymer unit in which the hydrolyzable silyl group and / or SiOH group is bonded to a side chain via an organic group having a urethane bond, and the polymer unit is the hydroxyalkyl The resin with a hard coat film according to claim 4 or 5, wherein a hydroxy group of a polymer unit having a group in a side chain is modified by a reaction with an isocyanate having a hydrolyzable silyl group and / or a SiOH group. substrate.   The resin substrate with a hard coat film according to any one of claims 1 to 6, wherein the silyl group-containing acrylic polymer has a weight average molecular weight of 5,000 to 300,000.   The resin substrate with a hard coat film according to any one of claims 1 to 7, wherein the silyl group-containing acrylic polymer further includes a polymer unit having a linear alkyl group having 2 to 16 carbon atoms.   The primer layer 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 molecular weight is 20 The absorption coefficient for light in the wavelength region of 350 nm to 380 nm of the ultraviolet absorber is an average value of 3.5 g / (mg · cm) to 100 g / (mg · cm). The resin substrate with a hard coat film according to any one of claims 1 to 8.   The resin substrate with a hard coat film according to claim 9, wherein the ultraviolet absorber is at least one selected from the group consisting of benzophenones, triazines, and benzotriazoles.   The hard coat film according to any one of claims 1 to 10, wherein the organopolysiloxane is composed of only T units and Q units, and the ratio of the number is T: Q = 90: 10 to 100: 0. With resin substrate. A method for producing a resin substrate with a hard coat film according to any one of claims 1 to 11,
Applying and drying a primer layer forming composition containing the acrylic polymer as a main component on at least one surface of the resin substrate to form the primer layer;
A silyl group-containing acrylic polymer that has 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 on the primer layer. Applying and drying an adhesive layer-forming composition containing, and forming the adhesive layer;
Applying and curing a hard coat layer forming composition containing the organopolysiloxane as a main component on the adhesive layer to form the hard coat layer;
A process for producing a resin substrate with a hard coat film, comprising:

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