WO2012086656A1

WO2012086656A1 - Resin substrate having a hard coat film and production method of resin substrate with a hard coat film

Info

Publication number: WO2012086656A1
Application number: PCT/JP2011/079554
Authority: WO
Inventors: 澁谷　崇; 今日子山本
Original assignee: 旭硝子株式会社
Priority date: 2010-12-20
Filing date: 2011-12-20
Publication date: 2012-06-28
Also published as: JPWO2012086656A1

Abstract

Disclosed is a structure comprising a silicon-based hard coat layer provided on a resin substrate with a primer layer therebetween; said structure improves scratch resistance and weather resistance properties such as weather-resistant adhesion and weather crack resistance. The production method of the resin substrate with a hard coat film involves: a step for coating at least one surface of the resin substrate with a primer layer-forming composition containing an acrylic polymer as the main component and for drying said composition to form a primer layer; a step for subjecting the surface of the aforementioned primer layer to corona discharge treatment; a step for performing silane coupling agent treatment by coating the surface of the primer layer, which has been subjected to corona discharge treatment, with a silane coupling agent composition containing a silane coupling agent as the main component and drying said composition; and a step for forming a hard coat layer by coating the surface of the aforementioned primer layer, which has undergone the aforementioned corona discharge treatment and silane coupling agent treatment, with a hard coat layer-forming composition containing organopolysiloxane as a main component and curing said composition.

Description

Resin substrate having hard coat film and method for producing resin substrate having hard coat film

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

In recent years, there has been an increasing demand for transparent resin plates instead of conventional inorganic glass plates as window materials for vehicles such as automobiles and window materials for building materials attached to buildings such as houses and buildings. 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 breakage, transparency, lightness, and ease. Since it is excellent in workability and the like, its use is 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 in place of the inorganic glass plate.

Therefore, for the purpose of improving the scratch resistance, weather resistance, etc. of the transparent resin plate, a film (hard coat layer) is formed on the surface of the transparent resin plate using various hard coat agents, particularly silicone hard coat agents. Has been proposed. At that time, in order to improve the adhesion between the hard coat layer and the transparent resin plate, it has also been proposed to interpose an adhesive layer such as a primer layer. Furthermore, a technique for further enhancing the adhesion effect by performing surface treatment such as corona treatment on the surface of such an adhesive layer has been reported (for example, see Patent Document 1).

However, the transparent resin plate provided with such a conventional hard coat layer has problems of weather resistance such as generation of cracks and deterioration of adhesion after long-term use. 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 silicone-based hard coat layer is lowered and peeling is likely to occur. Here, the weather resistance means that yellowing, coating film cracking, and peeling do not occur when used outdoors for a long period of time. Therefore, the evaluation requires a long time of several years to more than 10 years. Therefore, in general, weather resistance is evaluated by an accelerated weather resistance test in which ultraviolet rays, temperature and humidity environments are artificially set. Accordingly, a hard coat layer that can impart sufficient scratch resistance, weather resistance, etc. for a long period of time to the transparent resin plate is provided without adhesion deterioration even in an environment where ultraviolet irradiation and high humidity are repeated. Development of a resin substrate is demanded.

Japan Special Table 2005-536370 Publication

The present invention has been made to meet the above-mentioned demand, and in a resin substrate having a hard coat film in which a silicone-based hard coat layer is provided on a resin substrate via a primer layer, it has excellent scratch resistance and acceleration. Hard coat film with excellent weather resistance such as adhesion after weathering test (hereinafter also referred to as “weather resistance”) and cracking after accelerated weathering test (hereinafter also referred to as “weather cracking”) It aims at providing the resin substrate which has, and its manufacturing method.

In the method for producing a resin substrate having a hard coat film according to one embodiment of the present invention, a primer layer-forming composition containing an acrylic polymer as a main component is applied onto at least one surface of a resin substrate and dried. A step of forming a layer, a step of performing a corona discharge treatment on the surface of the primer layer, and applying a silane coupling agent composition containing a silane coupling agent as a main component on the surface of the primer layer subjected to the corona discharge treatment. And a step of applying a silane coupling agent treatment by drying, and a composition for forming a hard coat layer containing organopolysiloxane as a main component on the surface of the primer layer subjected to the corona discharge treatment and the silane coupling agent treatment And a step of forming a hard coat layer by applying and curing an object.

The resin substrate having a hard coat film according to another aspect of the present invention mainly comprises a primer layer containing an acrylic polymer as a main component and a cured product of organopolysiloxane on at least one surface of the resin substrate. A resin substrate having a hard coat film having a hard coat layer as a component in order from the resin substrate side, and a corona discharge treatment and a silane coupling agent treatment are sequentially applied to the hard coat layer side surface of the primer layer. It is characterized by being given.

In this specification, the “hard coat film” refers to a multi-layered film including a hard coat layer formed on a resin substrate. That is, in the present invention, the entire film having the primer layer and the hard coat layer is referred to as “hard coat film”.

According to the method for producing a resin substrate having a hard coat film of the present invention, it is possible to obtain a resin substrate having a hard coat film having excellent scratch resistance and weather resistance such as weather adhesion and weather cracking. . The resin substrate having the hard coat film of the present invention is excellent in scratch resistance and weather resistance such as weather adhesion and weather crack resistance.

Hereinafter, embodiments of the present invention will be described.

The resin substrate having the hard coat film of the present invention has a hard coat layer joined by a primer layer on at least one surface of the resin substrate, and a corona discharge treatment is performed on the hard coat layer side surface of the primer layer. And silane coupling agent treatment.

<Resin substrate>
As the resin constituting the resin substrate used in the present invention, polycarbonate resin, polystyrene resin, aromatic polyester resin, acrylic resin, polyester resin, polyarylate resin, polycondensate of halogenated bisphenol A and ethylene glycol, acrylic Thermoplastic resins such as urethane resins and halogenated aryl group-containing acrylic resins can be mentioned.

Among these, polycarbonate resins (such as aromatic polycarbonate resins) and acrylic resins (such as polymethyl methacrylate acrylic resins) are preferable, and polycarbonate resins are more preferable. Furthermore, among polycarbonate resins, aromatic polycarbonate resins are more preferable, and bisphenol A polycarbonate resins are particularly preferable.

The resin substrate may be a single-layered substrate containing two or more kinds of thermoplastic resins as described above, or may be a laminated substrate in which two or more layers are laminated using these resin substrates. Good. The shape of the resin substrate is not particularly limited, and may be a flat plate or curved. An example of the curved resin substrate is a three-dimensional molded body made by injection molding. Furthermore, the color tone of the resin substrate is preferably colorless and transparent or colored and transparent.

<Primer layer>
In the resin substrate having the hard coat film of the present invention, a primer layer is provided on at least one surface of the resin substrate. This primer layer is formed by applying and drying a composition (primer layer forming composition) containing an acrylic polymer as a main component on at least one surface of the resin substrate.

[Primer layer forming composition]
(1) Acrylic polymer The acrylic polymer that is the main component of the primer layer forming composition is, for example, a homopolymer or copolymer (copolymer) having at least one monomer having a methacrylic group (methacrylic acid ester) as a polymerization unit. Polymer).

As the methacrylic acid ester, a methacrylic acid alkyl ester having an alkyl group having 6 or less carbon atoms is preferable. Among them, methyl methacrylate (hereinafter sometimes referred to as “MMA”), n-butyl methacrylate, tert-methacrylic acid tert -Butyl, ethyl methacrylate and isobutyl methacrylate are preferred.

Specifically, the acrylic polymer includes homopolymers having methyl methacrylate, tert-butyl methacrylate, and ethyl methacrylate as monomer units, that is, polymethyl methacrylate, polytert-butyl methacrylate, polymethacrylic acid. A copolymer of ethyl or methyl methacrylate and at least one selected from the group consisting of n-butyl methacrylate, ethyl methacrylate, and isobutyl methacrylate is preferably used. The monomer unit of the acrylic polymer is particularly preferably methyl methacrylate, and a homopolymer or copolymer containing at least 90 mol% or more of polymerized units based on this methyl methacrylate is particularly preferably used as the acrylic polymer.

The acrylic polymer preferably has a mass average molecular weight Mw of 20,000 or more, more preferably 50,000 or more, from the viewpoint of sufficiently exhibiting adhesion and strength performance as a primer layer. . The acrylic polymer preferably has a mass average molecular weight Mw of 1 million or less. When the mass average molecular weight Mw is less than 20,000 or exceeds 1 million, the adhesion and strength performance as the primer layer may not be sufficiently exhibited. The mass average molecular weight Mw of the acrylic polymer is a value measured by using gel permeation chromatography with polystyrene as a standard substance.

Such acrylic polymers are also commercially available. In the present invention, these commercially available products, for example, Dianal LR269 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), mass average molecular weight: 100 , 2,000), LR248 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), mass average molecular weight: 155,000), and the like, which are commercially available as solutions previously dissolved in an appropriate solvent. Can be used. Further, Dianal BR80 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), mass average molecular weight: 90,000), Dianal BR88 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA)) , Mass average molecular weight: 430,000), M-4003 (trade name, manufactured by Negami Kogyo Co., Ltd., polymethyl methacrylate (PMMA), mass 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 content of the acrylic polymer in the primer layer forming composition is preferably 50% by mass to 98% by mass, and more preferably 70% by mass to 95% by mass. If the content is less than 50% by mass, the adhesion between the primer layer and the resin substrate is lowered, and peeling may occur. Moreover, when it exceeds 98 mass%, there exists a possibility that it may become difficult to fully improve the adhesiveness with respect to the hard-coat layer of a primer layer.
In the present invention, the primer layer forming composition containing an acrylic polymer as a main component contains 50% or more of an acrylic polymer with respect to the total amount of each component of the primer layer forming composition excluding the solvent. It shows that.
Note that “to” indicating the numerical range described above is used to mean that the numerical values described before and after that are used as the lower limit value and the upper limit value, unless otherwise specified. Are used with similar meanings.

(2) Other components In addition to the acrylic polymer, the primer layer forming composition further includes additives such as an ultraviolet absorber, a light stabilizer, a leveling agent, an antifoaming agent, and a viscosity modifier. You may include in the range which does not inhibit an effect.

In order to suppress yellowing of the resin substrate, it is preferable that the primer layer forming composition contains an ultraviolet absorber. As an ultraviolet absorber, the thing similar to the ultraviolet absorber contained in the composition for hard-coat layer formation mentioned later 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 part by mass to 50 parts by mass, and particularly preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the acrylic polymer.

Examples of the light stabilizer include hindered amines or nickel complexes such as nickel bis (octylphenyl) sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate. . These may be used individually by 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, and preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic polymer. Particularly preferred.

Further, the primer layer forming composition usually contains a solvent. The solvent is not particularly limited as long as (1) the solvent can stably dissolve the acrylic polymer. 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 be used individually by 1 type and may use 2 or more types together. The solvent is preferably at least one selected from n-butyl acetate, 1-methoxy-2-propanol, and diacetone alcohol.

The amount of the solvent is preferably 50 parts by mass to 10000 parts by mass, more preferably 100 parts by mass to 5000 parts by mass, and 100 parts by mass to 2000 parts by mass with respect to 100 parts by mass of the acrylic polymer. It is particularly preferred. The content of the nonvolatile component (solid content) in the primer layer forming composition is preferably 0.5% by mass to 75% by mass with respect to the total amount of the composition, and is 1% by mass to 50% by mass. More preferably, the content is 3% by mass to 30% by mass.

The primer layer forming composition can be obtained by uniformly mixing the various components described above by ordinary methods.

[Formation of primer layer]
The primer layer is formed by applying the composition prepared as described above onto a resin substrate and drying by heating. The method for applying the primer layer forming composition onto the resin substrate is not particularly limited, and spray coating, dip coating, flow coating, spin coating, and the like are used. The heating conditions for drying are not particularly limited, but are preferably 50 ° C. to 140 ° C. for 5 minutes to 3 hours.

The primer layer thus formed has a thickness of preferably 0.5 μm to 10 μm, and more preferably 2 μm to 8 μm. When the thickness of the primer layer is less than 0.5 μm, the weather resistance may be insufficient, and when it exceeds 10 μm, problems such as warping of the substrate may occur.

[Surface treatment of primer layer]
In the resin substrate having the hard coat film of the present invention, the surface modification treatment including (1) corona discharge treatment and (2) silane coupling agent treatment is performed in this order on the surface of the primer layer.

(1) Corona discharge treatment The corona discharge treatment is a treatment for activating the surface of the primer layer of the resin substrate disposed between the electrodes by discharging by applying a high voltage between the electrodes. Specifically, high-energy electrons and ions collide with the surface of the primer layer to generate radicals and ions, which react with surrounding ozone, oxygen, nitrogen, moisture, etc. Polar functional groups such as carboxyl groups, hydroxyl groups, cyano groups are introduced.

The effect of this corona discharge treatment varies depending on the distance between the electrode and the primer layer, applied voltage, moving speed, humidity, electrode type, primer layer type, etc., but in the present invention, for example, the electrode and primer layer the spacing and 1 mm ~ 5 mm, it is preferably subjected to the treatment discharge energy to the primer layer surface is ^{20W · min / m 2 ~ 500W} · min / m 2. When the discharge energy is less than 20 W · min / m ² , activation of the primer layer surface (specifically, introduction of polar functional groups such as carbonyl group, carboxyl group, hydroxyl group, cyano group, etc. on the primer layer surface) is insufficient. Thus, the weather adhesion between the hard coat layer and the primer layer becomes insufficient, and there is a possibility that good weather resistance cannot be imparted to the resin substrate having the finally obtained hard coat film. Moreover, if the discharge energy exceeds 500 W · min / m ² , the activation of the primer layer surface becomes excessive, and the primer layer surface deteriorates, which may reduce the adhesion between the hard coat layer and the primer layer. There is. The discharge energy is more preferably 30 W · min / m ² to 300 W · min / m ² , and particularly preferably 40 W · min / m ² to 200 W · min / m ² .

In order to perform the preferable corona discharge treatment as described above on the primer layer, a high frequency generating power source (generator), a high voltage transformer, and a corona discharge treatment apparatus including an electrode are used. The moving speed and the electrode width may be adjusted as appropriate. Specifically, for example, a method is used in which processing is performed under processing conditions of an interval between the electrode and the primer layer of 2 mm, power of 100 W, electrode width of 350 mm, and moving speed of 30 mm / s to 90 mm / s. Here, in the corona discharge treatment, for example, a substrate (resin substrate) on which a primer layer is formed is placed on a plate or belt that moves at a constant speed, and the electrode is oriented in a direction perpendicular to the moving direction of the plate or belt. Is performed by moving the plate or belt at a predetermined speed. The moving speed refers to the relative speed between the substrate on which the primer layer is formed and the electrode.

(2) Silane coupling agent treatment The silane coupling agent treatment is a reactive functional group possessed by a silane coupling agent by applying a silane coupling agent to the surface of the primer layer into which a polar functional group has been introduced by the corona discharge treatment. Is reacted with a polar functional group previously introduced by corona discharge treatment. By reacting the reactive functional group of the silane coupling agent with the polar functional group, the silane coupling agent is bonded to the surface of the primer layer with a strong force.

The silane coupling agent used in the silane coupling agent treatment is not particularly limited as long as it has a functional group that reacts with the polar functional group introduced in the corona discharge treatment. A silane coupling agent containing at least one selected from the group consisting of an epoxy group, a mercapto group, an isocyanate group, and a (meth) acryl group is preferable. In addition, the (meth) acryl group in this specification means an acryl group or a methacryl group. Similarly, (meth) acrylate means acrylate or methacrylate, and (meth) acrylic acid means acrylic acid or methacrylic acid.

Specifically, silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (Methacrylopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propylmethyldimethoxysilane, 3 Isocyanate propyl trimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, and the like. Of these, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane are preferable. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

In the silane coupling agent treatment, a composition prepared by dissolving the silane coupling agent in a solvent (hereinafter referred to as “silane coupling agent composition”) is applied to the surface of the primer layer subjected to corona discharge treatment and dried. Is done by.

The solvent used for dissolving the silane coupling agent is not particularly limited as long as it is a solvent capable of stably dissolving the silane coupling agent. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methoxyethanol, diacetone alcohol, 2-butoxyethanol, 1-methoxy Examples include alcohols such as -2-propanol and diacetone alcohol; hydrocarbons such as n-hexane, n-heptane, isoctane, benzene, toluene, xylene, gasoline, light oil, and kerosene. These may be used individually by 1 type and may use 2 or more types together. The amount of the solvent is preferably such that the non-volatile component (solid content) concentration in the silane coupling agent composition is 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 5% by mass. preferable.

The method for applying the silane coupling agent composition to the primer layer surface is not particularly limited, and spray coating, dip coating, flow coating, spin coating, and the like are used. The dip coating method is preferable from the viewpoint of processing uniformity and the like. The drying conditions are not particularly limited, but are preferably about 20 minutes to 1 hour at room temperature.

<Hard coat layer>
In the resin substrate having the hard coat film of the present invention, a hard coat layer made of a cured film containing organopolysiloxane is formed on the surface of the primer layer that has been subjected to the corona discharge treatment and the treatment with the silane coupling agent as described above. Is done. The hard coat layer is not particularly limited, and may be formed by applying a composition containing organopolysiloxane (a composition for forming a hard coat layer) as shown below to the surface of the primer layer and curing it by heating. preferable.

[Composition for forming hard coat layer]
(Organopolysiloxane)
The organopolysiloxane contained in the hard coat layer forming composition used for forming the hard coat layer of the present invention can be used without particular limitation as long as it is a curable organopolysiloxane.

Generally, organopolysiloxane is composed of silicon-containing bond units called M units, D units, T units, and Q units. Among these, curable organopolysiloxane is an oligomeric polymer mainly composed of T units or Q units, a polymer composed only of T units, a polymer composed only of Q units, T units and Q units. There is a polymer composed of In addition, 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 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 group that becomes a hydroxyl group by hydrolysis (hereinafter referred to as a hydrolyzable group). 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 the bond bond two silicon-containing bond units is 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 the Q unit is This is a unit having 0 organic group and 4 O ^* (or 4 O ^* 1 to 3 and 3 to 1 Z groups). Each silicon-containing bond unit is formed from a compound (hereinafter also referred to as a monomer) that does not have an oxygen atom (O ^* ) bonded to another silicon atom (has only a Z group). The monomer forming the T unit is hereinafter referred to as T monomer. Similarly, the monomers that form the M unit, the D unit, and the Q unit are referred to as the M monomer, the D monomer, and the Q monomer, respectively.

The monomer is represented by (R′—) _a Si (—Z) _4-a . Here, 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 capable of bonding 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 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, it may be a cured product in which almost no hydroxyl groups remain.

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 as compared with a chlorine atom and the like, and in the curable organopolysiloxane obtained by using a monomer in which the Z group is an alkoxy group, it is not present together with the hydroxyl group as a Z group. Often an alkoxy group of the reaction is present. 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 mainly composed of T units as main silicon-containing bond units are preferably used. Hereinafter, unless otherwise specified, curable organopolysiloxane is simply referred to as organopolysiloxane. Here, in this specification, organopolysiloxane having T unit as a main constituent unit (hereinafter also referred to as “organopolysiloxane (T)”) is M unit, D unit, T unit and Q unit. The ratio of the number of T units to the total number refers to an organopolysiloxane having a ratio of 50% to 100%. In the present invention, the ratio of the number of T units is preferably from 70% to 100%, particularly preferably an organopolysiloxane. An organopolysiloxane having a T unit ratio of 90% to 100% is used. 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 = 90-100: 10-0. Particularly preferably used.

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 an oxygen atom connecting silicon atoms)

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

The T unit having no oxygen atom (O ^* ) for bonding two silicon atoms and having only three —OX is hereinafter referred to as T0. T0 actually corresponds to an unreacted T monomer contained in the organopolysiloxane and is not a silicon-containing bond unit. This T0 is measured in the same manner as T1 to T3 in the analysis of units of T1 to T3.

T0 to T3 in the organopolysiloxane can be analyzed by measuring the bonding state of silicon atoms in the organopolysiloxane by nuclear magnetic resonance analysis ( ²⁹ Si-NMR). The ratio of the number of T0 to T3 is determined from the peak area ratio of ²⁹ Si-NMR. -OX in the organopolysiloxane molecule can be analyzed by infrared absorption analysis. The ratio of the number of hydroxyl groups and alkoxy groups bonded to silicon atoms 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 the T monomer, T1, and T2 may differ depending on the difference in R even if the three —OXs in the T monomer are the same.

The organopolysiloxane (T) is preferably produced from at least one T monomer represented by R—Si (—OY) ₃ . 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, and 7 carbon atoms. ˜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. The functional group is preferably a hydroxyl group, mercapto group, carboxyl group, epoxy group, amino group, cyano group or the like. 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, a 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, a functional group-containing organic group or the like includes a category of compounds called silane coupling agents.

Specific examples of the substituted organic group include 3-chloropropyl group, 3,3,3-trifluoropropyl group, 3-mercaptopropyl group, p-mercaptomethylphenylethyl group, 3-acryloyloxypropyl group, 3-methacryloyl group. Oxypropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl)- A 3-aminopropyl group, a 2-cyanoethyl group and the like can be mentioned.

A particularly preferred monovalent organic group as R is an alkyl group having 1 to 4 carbon atoms. The organopolysiloxane (T) is preferably an organopolysiloxane obtained by using a T monomer having an alkyl group having 1 to 4 carbon atoms alone or two or more thereof. An organopolysiloxane obtained by using one or more T monomers having an alkyl group having 1 to 4 carbon atoms and a small amount of other T monomers as the organopolysiloxane (T) is also preferable. The proportion of other T monomers is preferably 30 mol% or less, particularly preferably 15 mol% or less, based on the total amount of T monomers. 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. Of these, methyltrimethoxysilane and ethyltrimethoxysilane are preferable.

Specific examples of the T monomer having a substituted organic group include, for example, 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-aminopropyl Pills triethoxysilane, N- (2- aminoethyl) -3-aminopropyltrimethoxysilane, 3-cyano-ethyl trimethoxysilane, and the like.

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 ′ may be the same or different. In the case of being identical, an alkyl group having 1 to 4 carbon atoms is preferred. 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 a functional group-containing organic group. The Z group is preferably an alkoxy group having 1 to 4 carbon atoms, an acetoxy group, or the like.

Examples of the D monomer include dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiacetoxysilane, 3-chloropropylmethyldimethoxysilane, 3, 3, 3-trifluoropropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldi Examples include ethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-cyanoethylmethyldimethoxysilane.

In the Q monomer (a = 0) represented by (R′—) _a Si (—Z) _4-a , the four Z groups may be different but are usually the same. The Z group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

Examples of the Q monomer include tetramethoxysilane, tetraethoxysilane, tetra n-propoxy silane, tetra n-butoxy silane, tetra sec-butoxy silane, tetra t-butoxy silane, and the like.

The organopolysiloxane (T) used in the present invention is obtained by subjecting the above T monomer and the like to partial hydrolysis condensation. Usually, this reaction is performed by heating T monomer or the like and water in a solvent. A catalyst is preferably present in the reaction system. The desired 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 a target organopolysiloxane, or a target organopolysiloxane can be produced using a commercially available organopolysiloxane.

As the catalyst, an acid catalyst is preferable. Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p- An organic acid such as toluenesulfonic acid may be mentioned. Of these, acetic acid is preferred. As the solvent, a hydrophilic organic solvent is preferable, and an alcohol solvent is more preferable. Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, diacetone alcohol, 2-butoxyethanol and the like. It is done. The reaction temperature can be reacted at room temperature when a catalyst is present. Usually, an appropriate temperature is employed from the reaction temperature of 20 ° C. to 80 ° C. according to the purpose.

The hydrolysis condensation reaction is a reaction in which T1 is generated from T0 (T monomer), T2 is generated from T1, and T3 is generated from T2. Condensation reaction in which at least one hydrolyzable group is converted to a hydroxyl group by T0 to T1, a condensation reaction in which at least one of two —OX is a hydroxyl group, T1 to T2 is generated, and —OX is a hydroxyl group It is considered that the respective reaction rates of the condensation reactions generated from T2 to T3 become 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. Among the organopolysiloxanes (T) used in the present invention, the organopolysiloxane (a) described later has a relatively small amount of T0 and T1, and the ratio of the amounts of T2 and T3 is within a specific range. It is a high molecular weight organopolysiloxane, and such an organopolysiloxane can be produced by selecting relatively mild reaction conditions.

The reactivity of the above condensation reaction varies depending on R, and when R is different, the reactivity of the hydroxyl group also varies. 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 becomes difficult to obtain a high ratio of the amount of hydroxyl groups to alkoxy groups in the organopolysiloxane. For this reason, the alkoxy group which is an OX group is preferably a highly reactive alkoxy group, that is, an alkoxy group having a low carbon number, and most preferably a methoxy group. When the reactivity of the hydrolyzable group is sufficiently high, an organopolysiloxane having a high proportion of hydroxyl groups can be obtained from an organopolysiloxane having a high proportion of hydrolyzable groups without much progress of the condensation reaction.

In the composition for forming a hard coat layer used in the present invention, one kind of curable organopolysiloxane (T) thus obtained may be blended alone, or two or more kinds may be blended together. Is also possible. The combination of organopolysiloxane (a) and organopolysiloxane (b) will be described below as a particularly preferred combination of organopolysiloxane (T) from the viewpoint of scratch resistance. The curable organopolysiloxane used in the present invention is described below. It 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 units T1 to T3 in 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. Furthermore, the mass average molecular weight of the organopolysiloxane (a) is 800 to 8000. 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), (T2 + T3) / (T1 + T2 + T3) is preferably in the range of 0.85 to 1.00, 0.90 or more and less than 1.00 It is more preferable that For T3 / T2, the preferred range is 2.0 to 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 used in combination in the composition for forming a hard coat layer according to the present invention, the scratch resistance of the finally obtained hard coat layer can be improved.

(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 a composition for forming a hard coat layer is formed by combining the organopolysiloxane (b) and the organopolysiloxane (b), the curing reaction during the formation of the cured film is accelerated. In addition, alkoxy groups left unreacted during the formation of the cured film may cause a decrease in scratch resistance of the finally obtained hard coat layer, and if post-curing progresses, it may cause micro cracks. The higher the proportion of hydroxyl groups compared to the 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) during the formation of a cured film ( In the network structure), a part of the organopolysiloxane (a) is not incorporated and it is easy to bleed out, etc., so that the crosslink density is reduced, the wear resistance is not obtained, and the curing does not proceed sufficiently. There is a risk of problems such as becoming.

The mass average molecular weight of the organopolysiloxane (a) is 800 to 8000, preferably 1000 to 6000. When the weight average molecular weight of the organopolysiloxane (a) is within this range, the organopolysiloxane (a) and the organopolysiloxane (b) are used in combination in the composition for forming a hard coat layer of the present invention. The scratch resistance of the finally obtained 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% by mass or more of the monomer is methyltrialkoxysilane, and preferably the alkoxy group has 1 to 4 carbon atoms. However, a small amount of 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 of producing the organopolysiloxane (a), as described above, a T monomer or the like is subjected to a hydrolysis condensation reaction in a solvent in the presence of an acid catalyst. The water required for the hydrolysis is usually 1 equivalent to 10 equivalents, preferably 1.5 equivalents to 7 equivalents, more preferably 3 equivalents to 5 equivalents, relative to 1 equivalent 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. The amount of the acid catalyst used is preferably from 0.1 to 50 parts by weight, particularly preferably from 1 to 20 parts by weight, based on 100 parts by weight of the monomer. As the solvent, the alcohol solvent is preferable, and methanol, ethanol, 2-propanol, 1-butanol, and 2-butanol are particularly preferable from the viewpoint of good solubility of the resulting organopolysiloxane (a). preferable.

Usually, the reaction temperature is 20 ° C. 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 ° C. to 80 ° C. for 1 hour to several days in order to stabilize the resulting organopolysiloxane.

Organopolysiloxane (a) can also be produced from commercially available organopolysiloxane. Since the commercially available organopolysiloxane is usually an organopolysiloxane having a higher proportion of alkoxy groups than the hydroxyl group, in particular, except for the above (B) / (A), commercially available similar to the desired organopolysiloxane (a). It is preferable to produce the organopolysiloxane (a) by increasing the proportion of hydroxyl groups by hydrolysis reaction using the above organopolysiloxane.

Examples of commercially available organopolysiloxane that can be used as a raw material for the organopolysiloxane (a) include the following organopolysiloxane that is a partial hydrolysis-condensation product of methyltrimethoxysilane. It should be noted that “ND” is not more than a detected amount when the ²⁹ Si-NMR peak area ratio is measured using a nuclear magnetic resonance analyzer, manufactured by JEOL Ltd., ECP400 (trade name). Shown (the same applies below).

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, mass average molecular weight Mw = 4720, number average molecular weight Mn = 1200, 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, Si—OH group-derived peaks were not confirmed by FT-IR, Only substantially SiO—CH ₃ exists. Mw = 1240, Mn = 700, Mw / Mn = 1.77.

When producing the organopolysiloxane (a) from the above-mentioned commercially available organopolysiloxane, it is preferable to hydrolyze the alkoxy group of the commercially available organopolysiloxane mainly in the presence of an acid catalyst. For example, 0 to 10 times (mass) of a solvent is added to a commercially available organopolysiloxane, stirred well, and then an acid aqueous solution having a concentration of about 0.1 to 70% by mass is added to form 15 ° C. Examples of the method include stirring at a temperature of ˜80 ° C., preferably 20 ° C. to 70 ° C., for 1 hour 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) is an organopolysiloxane having a mass average molecular weight of 1/10 to 1 / 1.5 times the mass average molecular weight of the organopolysiloxane (a). The organopolysiloxane (b) is an organopolysiloxane having a mass average molecular weight smaller than that of the combined organopolysiloxane (a), 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 mass average molecular weight 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) When the mass average molecular weight of b) is less than 1.5 times, the toughness of the finally obtained hard coat layer is lowered, which causes cracks. Further, when the mass average molecular weight of the organopolysiloxane (b) is less than 1/10 times the mass average molecular weight of the organopolysiloxane (a), in other words, the mass average molecular weight of the organopolysiloxane (a) is the organopolysiloxane (b). When the weight average molecular weight of 10) exceeds 10 times, the scratch resistance of the finally obtained hard coat layer is lowered, and there is a possibility that 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 a ratio of the number of these units, T0: T1: T2: T3 = 0 to 5: 0 to An organopolysiloxane in the range of 50: 5 to 70:10 to 90. A large ratio 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, the composition for forming a hard coat layer containing this and the organopolysiloxane (a) is used for heat curing when forming a cured film. The occurrence of cracks tends to increase. 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, the composition for forming a hard coat layer containing this and the organopolysiloxane (a) is used, and at the time of thermosetting when forming a cured film, Since appropriate crosslinking reaction becomes difficult, a cured film may not be formed, and a hard coat layer having sufficient scratch resistance may not be finally 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 when the ²⁹ Si-NMR peak area ratio is measured using an ECP400 (trade name) manufactured by JEOL Ltd., manufactured by JEOL Ltd. Indicates the following (the same applies hereinafter).

Tosgard 510 (trade name, manufactured by Momentive Performance Materials); molecular weight: Mn = 1370, Mw = 1380, Mw / Mn = 1.01. (Number of T units): (Total amount of each of M units, D units, and Q units) = 99.9 or more: ND. T0: T1: T2: T3 = ND: 2: 36: 62.

KP851 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); molecular weight: Mn = 1390, Mw = 1400, Mw / Mn = 1.01, (number of T units): (number of M units, D units, and Q units) Total amount) = 99.9 or more: ND. T0: T1: T2: T3 = trace: 21: 58: 21.

The ratio of the content of the organopolysiloxane (b) to the organopolysiloxane (a) is preferably 1.5 to 30 times, more preferably 2 to 15 times in terms of mass ratio. If both are contained at such a ratio, the organopolysiloxane three-dimensional crosslinked structure formed by the curing reaction is partially composed of the (a) component organopolysiloxane in the organopolysiloxane (b) -based three-dimensional crosslinked structure. Thus, the scratch resistance of the finally obtained hard coat layer can be improved.

The composition for forming a hard coat layer used in the present invention contains the curable organopolysiloxane, preferably organopolysiloxane (T). The content of the organopolysiloxane in the composition for forming a hard coat layer is preferably 50% by mass to 100% by mass with respect to the total amount of the composition components excluding the solvent (hereinafter also referred to as “nonvolatile components”). More preferably, it is from 95% by mass. The amount of this non-volatile component is measured based on the mass change after being held at 150 ° C. for 45 minutes.
In the present invention, the composition for forming a hard coat layer containing an organopolysiloxane as a main component is 50% or more of the organopolysiloxane with respect to the total amount of each component of the composition for forming a hard coat layer excluding the solvent. It shows that it contains.

(Optional component)
The hard coat layer forming composition may contain various additives in addition to the organopolysiloxane. For example, in order to further improve the scratch resistance of the hard coat layer, it is preferable to add silica fine particles, and it is more preferable to add 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 blended with 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, a T monomer and, if necessary, water or an acid catalyst are added to colloidal silica, and the organopolysiloxane can be produced in the colloidal silica dispersion medium as described above. 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 used in the present invention preferably have an average particle size (BET method) of 1 nm to 100 nm. If the average particle diameter exceeds 100 nm, the particles diffusely reflect light, and thus the value of the haze value of the resulting hard coat layer increases, which may be undesirable in terms of optical quality. The average particle size is more preferably 5 nm to 40 nm. This is for imparting scratch resistance to the hard coat layer and maintaining the transparency of the hard coat layer. The colloidal silica may be either water-dispersed or organic solvent-dispersed, but is preferably water-dispersed. It is more preferable to use colloidal silica dispersed in an acidic aqueous solution. Colloidal silica may contain inorganic fine particles other than silica fine particles such as alumina sol, titanium sol, and ceria sol.

The content of the silica fine particles is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 40% by mass with respect to the total amount of the composition components (nonvolatile components) excluding the solvent. If the content of the silica fine particles is less than 1% by mass, sufficient scratch resistance may not be ensured in the obtained hard coat layer, and if the content exceeds 50% by mass, the organopolysiloxane in the nonvolatile component may not be secured. The ratio becomes too low, making it difficult to form a cured film by thermal curing of the organopolysiloxane, cracks in the final hard coat layer, and aggregation of silica particles, resulting in transparency of the hard coat layer There is a risk of problems such as lowering.

Additives such as antifoaming agents and viscosity modifiers may be added to the hard coat layer forming composition for the purpose of improving coatability, and adhesion for improving the adhesion to the primer layer. Additives such as imparting agents may be blended, and additives such as leveling agents may be blended for the purpose of improving coatability and 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. In the composition for forming a hard coat layer, a dye, a pigment, a filler, and the like may be blended within a range that does not impair the object of the present invention.

The hard coat layer forming composition may further contain a curing catalyst. Examples of the curing catalyst include lithium metal salts such as aliphatic carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, succinic acid, etc.); alkali metal salts such as sodium salts and potassium salts; benzyltrimethylammonium salts, tetra Quaternary ammonium salts such as methylammonium salt and tetraethylammonium salt; metal alkoxides and chelates such as aluminum, titanium and cerium; ammonium perchlorate, ammonium chloride, ammonium sulfate, sodium acetate, imidazoles and their salts, trifluoromethylsulfonic acid Examples include ammonium and bis (toluomethylsulfonyl) bromomethylammonium. 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 blending amount of the curing catalyst is less than 0.01 parts by mass, it is difficult to obtain a sufficient curing rate, and when it exceeds 10 parts by mass, the storage stability of the composition for forming a hard coat layer is reduced or a precipitate is formed. Sometimes.

In addition, it is preferable to add an ultraviolet absorber to the hard coat layer forming composition in order to suppress yellowing of the 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. Further, in order to prevent the ultraviolet absorber from bleeding out from the finally obtained hard coat layer, an ultraviolet absorber having a trialkoxysilyl group may be used. The ultraviolet absorber having a trialkoxysilyl group is converted into a hydroxyl group by a hydrolysis reaction during the formation of a cured film by thermal curing of the organopolysiloxane, and then incorporated into the cured film by a dehydration condensation reaction. Bleeding out of the absorbent from the hard coat layer can be suppressed. Specific examples of the trialkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group. The blending amount of the ultraviolet absorber in the hard coat layer forming composition is preferably 0.1 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the organopolysiloxane. Part is particularly preferred.

Further, in the present invention, in order to prevent gelation of the composition for forming a hard coat layer at room temperature and to enhance the storage stability, the pH of the composition for forming a hard coat layer is set to 3.0 to 6.0. It is preferable to adjust to 4.0 to 5.5, and it is more preferable to adjust to 4.0 to 5.5. 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. Examples of the pH adjustment method include addition of an acid and adjustment of the content of the curing catalyst. Acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluene Organic acids such as sulfonic acids are used.

The composition for forming a hard coat layer is usually prepared in a form in which organopolysiloxane, which is an essential component, and various additives, which are optional components, are dissolved and dispersed in a solvent. It is important that all the non-volatile components in the hard coat layer-forming composition described above are stably dissolved or dispersed in the solvent. For this purpose, the solvent contains at least 20% by mass of alcohol, preferably 50% by mass or more. It is preferable to contain.

Examples of alcohols used in such solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, and 2-ethoxyethanol. , Diacetone alcohol, and 2-butoxyethanol. Among these, alcohols having a boiling point of 80 ° C. to 160 ° C. are preferable from the viewpoint of good solubility of the organopolysiloxane and good coating properties. Specifically, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, diacetone alcohol, and 2 -Butoxyethanol is preferred.

The solvent used in the composition for forming a hard coat layer includes, for example, a lower alcohol generated by hydrolyzing a raw material monomer, for example, an alkyltrialkoxysilane, in the production of an organopolysiloxane, a water dispersion type In the case of using water in colloidal silica that does not participate in the hydrolysis reaction, or colloidal silica in an organic solvent dispersion system, the dispersed organic solvent is also included.

Furthermore, in the composition for forming a hard coat layer, a solvent other than the above may be used in combination with a solvent other than alcohol that can be mixed with water / alcohol. Examples of such a solvent include 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 hard coat layer forming composition is preferably 50 parts by weight to 3000 parts by weight, and more preferably 150 parts by weight to 100 parts by weight with respect to 100 parts by weight of all nonvolatile components in the hard coat layer forming composition. More preferably, it is 2000 parts by mass.

The composition for forming a hard coat layer can be obtained by uniformly mixing the various components described above by an ordinary method.

[Formation of hard coat layer]
The hard coat layer was prepared by applying the composition for forming a hard coat layer prepared as described above onto the primer layer subjected to the corona discharge treatment and the silane coupling agent treatment in this order. It is formed by heat-curing the coating film.

The method for applying the hard coat layer forming composition onto the primer layer is not particularly limited, and a normal coating method such as a spray coating method, a dip coating method, a flow coating method, or a spin coating method is used. It is preferable to appropriately adjust the viscosity, solid content concentration and the like of the composition for forming a hard coat layer according to the coating method to be used.

The thickness of the coating film formed by applying the hard coat layer forming composition to the surface of the primer layer is affected by the solid content concentration in the composition. It is preferable to adjust the solid content appropriately so that the film thickness after curing is within a predetermined range.

The film thickness of the cured film applied on the primer layer is preferably 0.1 μm to 20 μm, more preferably 1 μm to 10 μm, and more preferably 2 μm to 10 μm in the state after curing described below. It is particularly preferred. If the thickness of the hard coat layer is too small, it may be difficult to ensure sufficient scratch resistance and weather 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 and weather resistance, the thickness of the cured film (that is, the thickness of the hard coat layer) is 0.1 μm to 20 μm. Preferably there is. This film thickness means the thickness when a hard coat layer is formed alone on a substrate such as a resin substrate.

The organopolysiloxane is cured by subjecting the coating film of the hard coat layer forming composition thus formed to a heat treatment. In the present specification, “the hard coat layer forming composition is sometimes cured” means that the organopolysiloxane contained in the hard coat layer forming composition is cured. Prior to this heat treatment, a drying operation may be provided as necessary.

For drying, the coating film formed on the primer layer as described above is usually placed at a room temperature or under a temperature condition lower than the thermal deformation temperature of the resin substrate for a certain period of time, whereby a part or all of the solvent in the coating film is used. Is an operation to be removed. Examples of the solvent drying conditions include a condition of holding at a temperature of 0 ° C. to 60 ° C. for 10 minutes to 10 hours. Alternatively, the solvent may be removed by vacuum drying or the like while adjusting the degree of vacuum.

After such optional drying, the coating film is subjected to heat treatment to form a cured film. This heat treatment can be a treatment similar to the treatment usually performed to condense and cure the hard coat layer forming composition.

It is preferable that the heat treatment is performed at a high temperature within a range where there is no problem with the heat resistance of the resin substrate because curing can be completed more quickly. However, for example, when an organopolysiloxane having a methyl group as a monovalent organic group is used, the methyl group is eliminated by thermal decomposition when the temperature during heat curing is 250 ° C. or higher. Accordingly, the heating temperature is preferably 50 ° C. to 200 ° C., more preferably 80 ° C. to 160 ° C., and particularly preferably 100 ° C. to 140 ° C. As a heating means, a natural convection type thermostat, a constant temperature drier, a hot air circulation drier, a blower drier, a method of heating with a vacuum drier, or the like is used. An electric furnace or the like can also be used. Furthermore, a heating means using an infrared lamp can be used as appropriate. These heating means may be used alone or in combination of two or more.

The heat treatment time is not particularly limited as long as the organopolysiloxane contained in the composition for forming a hard coat layer constituting the coating film is sufficiently condensed and cured to form a three-dimensional structure by siloxane bonds. 10 minutes to 4 hours are preferable, 20 minutes to 3 hours are more preferable, and 30 minutes to 2 hours are particularly preferable.
<Topcoat layer>

In the resin substrate having the hard coat film of the present invention, in order to further improve the scratch resistance, weather resistance, film strength and the like, a top coat layer whose main component is SiO ₂ may be applied on the hard coat layer. Good. As a method for forming the top coat layer whose main component is SiO ₂ , a technique of applying poly (perhydro) silazane on the hard coat layer and curing it, or a technique such as vapor deposition or sputtering can be used.

<Resin substrate having a hard coat film>
In the resin substrate having the hard coat film of the present invention, since the hard coat layer is provided on the surface of the primer layer subjected to the corona discharge treatment and the silane coupling agent treatment in order, the conventional surface treatment is performed. Compared to the case where the hard coat layer is provided via a primer layer that is not provided, the weather resistance adhesion between the hard coat layer and the primer layer is improved. As a result, good scratch resistance and high weather resistance of the hard coat layer can be imparted to the resin substrate.

The reason why the adhesion between the primer layer and the hard coat layer is improved by the surface treatment as described above is considered as follows. That is, by performing corona discharge treatment on the primer layer, as described above, high-energy electrons and ions collide with the surface of the primer layer to generate radicals and ions, and the surrounding ozone, oxygen, nitrogen, moisture, etc. React to introduce a polar functional group such as a carbonyl group, a carboxyl group, a hydroxyl group, or a cyano group. Next, the surface of the primer layer into which the polar functional group has been introduced in this manner is treated with a silane coupling agent, so that the reactive functional group of the silane coupling agent reacts with the introduced polar functional group and chemically. Then, when the hard coat layer is provided, the hydrolyzable silyl group of the silane coupling agent and the silanol group or hydrolyzable silyl group of the organopolysiloxane constituting the hard coat layer undergo a hydrolysis reaction, Dehydration condensation. Any bond between the polar functional group introduced into the primer layer and the reactive functional group of the silane coupling agent, and the bond between the hydrolyzable silyl group of the silane coupling agent and the silanol group or hydrolyzable silyl group of the organopolysiloxane Is a strong bond by a covalent bond, and the bond is rarely broken by moisture. Therefore, even under high humidity conditions, the adhesion of the hard coat layer to the primer layer does not decrease. On the other hand, in the case of a primer layer not provided with the surface as described above, it is only bonded to the hard coat layer by hydrogen bonding or the like. The bond strength due to hydrogen bonds is much weaker than covalent bonds and is easily cleaved by moisture. Therefore, the adhesiveness of the hard coat layer to the primer layer decreases under high humidity conditions. For this reason, in the resin substrate having the hard coat film of the present invention in which the hard coat layer is provided on the surface-treated primer layer as described above, the conventional hard coat layer is provided on the primer layer that is not surface-treated. Compared to a resin substrate having a hard coat film, it is considered that the weather resistance adhesion under a high humidity condition is greatly improved.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 6 are examples, and examples 7 and 8 are comparative examples. The organopolysiloxane was analyzed by the following method.

(1) Number of silicon atom-bonded hydroxyl groups (B) / Number of silicon atom-bonded alkoxy groups (A)
Hereinafter, since the organopolysiloxane used in the 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 determined by the method was used. Infrared absorption spectrometer (FT-IR, Thermo Fisher Scientific Co., Model: Avatar / Nicolet FT-IR360) using, Si absorption and 900cm around ^-1 derived from SiO-CH ₃ in the vicinity of 2860Cm ^-1 The ratio of Si—OH / SiO—CH ₃ was determined from the area ratio of absorption derived from —OH.

(2) Analysis of bonding state of silicon atom in organopolysiloxane Bonding state of silicon atom in organopolysiloxane contained in the composition for forming a hard coat layer, specifically, M unit, D unit, T unit, The proportion of Q units and the ratio of T0 to T3 were determined from the ²⁹ Si-NMR peak area ratio using a nuclear magnetic resonance analyzer ( ²⁹ Si-NMR: ECP400, manufactured by JEOL Ltd.). It was. The measurement conditions were a polytetrafluoroethylene (PTFE) 10 mmφ sample tube, a probe: T10, a resonance frequency of 79.42 MHz, a pulse width of 10 μsec, a waiting time of 20 sec, an accumulation count of 1500 times, a relaxation reagent: Cr (acac) ₃ of 0. 1% by mass, external standard sample: tetramethylsilane. The chemical shift of ²⁹ Si-NMR derived from each structure is as follows in the case of methyl-based organopolysiloxane.
(M unit to Q unit)
M unit: 15 ppm to 5 ppm,
D unit: −15 ppm to −25 ppm,
T unit: -35 ppm to -75 ppm,
Q unit: -90 ppm to -130 ppm.
(T0 to T3)
T0: −40 ppm to −41 ppm,
T1: -49 ppm to -50 ppm,
T2: -57 ppm to -59 ppm,
T3: -66 ppm to -70 ppm.

(3) Number average molecular weight Mn, mass 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).

[Preparation of primer layer forming composition]
Polymethyl methacrylate (PMMA) (Mn = 120,000, Mw = 340,000, Mw / Mn = 2.8) and ultraviolet absorber dibenzoresorcinol (DBR; manufactured by Clariant, extinction coefficient ε (350-380) ave : 5.5) is mixed with 10 parts by weight of DBR with respect to 100 parts by weight of PMMA and dissolved in a mixed solvent of 1-methoxy-2-propanol: diacetone alcohol = 85: 15 (mass ratio). As a result, a primer layer forming composition (Pr-1) having a nonvolatile content of 10% by mass was obtained.

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 + HZ 2000), eluent: THF Asked.

[Preparation of composition for forming hard coat layer]
In a 0.2 L flask, methyl silicone resin KR-500 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd .; the peak derived from the Si—OH group was not confirmed by FT-IR, but only substantially SiO—CH ₃ . Unit abundance ratio T0: T1: T2: T3 = ND: 15: 58: 27, Mn = 700, Mw = 1240, Mw / Mn = 1.77) 10 g and 1-butanol 10 g were added and stirred well. Acetic acid 10 g and ion-exchanged water 10 g were added and stirred well. This solution was stirred at 40 ° C. for 1 hour to obtain an organopolysiloxane (a) composition (MSi-1).

When the organopolysiloxane (a) was compared with the raw material KR-500 by FT-IR, it was confirmed that the peak derived from the SiO—CH ₃ group decreased and the peak derived from the Si—OH group appeared. did. The ratio of Si—OH / SiO—CH ₃ of the organopolysiloxane (a) obtained from the peak area ratio of FT-IR was 41.0. Organopolysiloxane (a) consists of only T units, and the abundance ratio of each T unit determined from the chemical shift of ²⁹ Si-NMR is T0: T1: T2: T3 = ND: 1.1: 30.1: 68. .8. Moreover, Mn was 520, Mw was 1150, and Mw / Mn was 2.22.

Further, 167 g of water-dispersed colloidal silica (pH 3.1, solid content 20 mass%) having an average particle diameter of about 30 nm and 14 g of acetic acid were added to a 1 L flask, and 136 g of methyltrimethoxysilane was further added. Upon stirring for 1 hour, the pH of the mixture stabilized at 4.5. This mixture was aged at 25 ° C. for 4 days and partially hydrolyzed and condensed to obtain a composition containing organopolysiloxane (b).

This composition has a non-volatile component of 40% by mass, and the organopolysiloxane (b) contained has a bond structure mainly composed of T units (the number of T units: the total number of M units, D units, and Q units). The abundance ratio of each T unit obtained from the chemical shift of ²⁹ Si-NMR was T0: T1: T2: T3 = ND: 2: 54: 44. In the organopolysiloxane (b), there is almost no monomeric T0 form [R—Si (OH) ₃ ] (R is a monovalent organic group), and the raw material methyltrimethoxysilane is an oligomeric organopolysiloxane. It was confirmed that it was almost completely converted to siloxane. Mn of organopolysiloxane (b) was 400, Mw was 670, and Mw / Mn was 1.68.

4 parts by mass of a benzophenone-based ultraviolet absorber was added to 100 parts by mass of the organopolysiloxane (b) obtained above and aged at 25 ° C. for 24 hours or more. Using a mixed solvent (1-butanol: isopropanol: methanol: 1-methoxy-2-propanol = 40: 40: 15: 5 (mass ratio)) as a diluting solvent, a nonvolatile content of 25% by mass (150 ° C., 45 minutes) An organopolysiloxane (b) composition (PSi-1) having a viscosity of 4.4 mPa · s was prepared.

To 80 parts of the organopolysiloxane (a) composition (MSi-1), 20 parts of the organopolysiloxane (b) composition (PSi-1) are added and mixed uniformly. HC-1) was obtained.

[Preparation of Silane Coupling Agent Composition]
(Preparation Example 1)
3-Glycidoxypropyltrimethoxysilane was dissolved in 2-propanol to prepare a silane coupling agent composition (SiC-1) having a solid content of 0.25% by mass.
(Preparation Example 2)
3-Mercaptopropyltrimethoxysilane was dissolved in 2-propanol to prepare a silane coupling agent composition (SiC-2) having a solid content of 0.25% by mass.
(Preparation Example 3)
3-Isocyanatopropyltrimethoxysilane was dissolved in hexane to prepare a silane coupling agent composition (SiC-3) having a solid content of 0.25% by mass.

[Preparation of resin substrate sample having hard coat film]
(Example 1)
After a 3 mm thick polycarbonate resin plate (trade name Carboglass (registered trademark) polish clear, manufactured by Asahi Glass Co., Ltd.) is coated with the primer layer forming composition (Pr-1) by the dip method and allowed to stand at 25 ° C. for 20 minutes. Then, it was cured by heating at 120 ° C. for 30 minutes to form a primer layer having a thickness of 4 μm.

Next, with respect to the surface of the primer layer, using a corona discharge treatment device (generator: HV2010 manufactured by TANTEC, transformer: HT10-280IL manufactured by TANTEC, electrode: SUS wire (350 mm width)), power 100 W, distance 2 mm, Corona discharge treatment was performed under the condition of a moving speed of 90 mm / s. Discharge energy for the primer layer surface by this treatment was 53W · min / ^{m 2.}

Next, a silane coupling agent composition (SiC-1) was coated on the primer layer subjected to the corona discharge treatment by a dipping method (pulling speed 10 mm / s) and dried at room temperature for 30 minutes.

Next, a hard coat layer-forming composition (HC-1) was coated on the primer layer that had been subjected to corona discharge treatment and silane coupling agent treatment by a dip method, left at 25 ° C. for 20 minutes, and then 120 ° C. And cured for 1 hour to form a hard coat layer having a thickness of 3 μm, and a resin substrate sample was produced. This resin substrate sample has a primer layer and a hard coat layer on both sides of a polycarbonate resin plate.

(Example 2)
Example 1 except that the primer layer thickness was 5 μm, the corona discharge treatment conditions were such that the power was 100 W, the moving speed was 30 mm / s, and the discharge energy for the primer layer surface was 159 W · min / m ^2. Thus, a resin substrate sample was produced.

(Example 3)
A resin substrate sample was produced in the same manner as in Example 1 except that the silane coupling agent composition (SiC-2) was used instead of the silane coupling agent composition (SiC-1).

(Example 4)
A resin substrate sample was produced in the same manner as in Example 2 except that the silane coupling agent composition (SiC-2) was used instead of the silane coupling agent composition (SiC-1).

(Example 5)
A resin substrate sample was produced in the same manner as in Example 1 except that the silane coupling agent composition (SiC-3) was used instead of the silane coupling agent composition (SiC-1).

(Example 6)
A resin substrate sample was produced in the same manner as in Example 2 except that the silane coupling agent composition (SiC-3) was used instead of the silane coupling agent composition (SiC-1).

(Example 7)
A resin substrate sample was produced in the same manner as in Example 2 except that the corona discharge treatment and the silane coupling agent treatment were not performed.

(Example 8)
A resin substrate sample was produced in the same manner as in Example 2 except that the silane coupling agent treatment was not performed.

[Evaluation of resin substrate sample having hard coat film]
The following items were evaluated for the resin substrate samples obtained in Examples 1 to 8 above.

<1> Film thickness (primer layer and hard coat layer)
The film thicknesses of the hard coat layer and the primer layer in each sample were measured using an interference film thickness measuring device (trade name Solid Lambda Thickness, manufactured by Spectra Corp.). In addition, the refractive index used the value of n = 1.46 (hard coat layer) and n = 1.56 (primer layer).

<2> Initial appearance The entire coating film including the hard coat layer and the primer layer (hereinafter referred to as a hard coat film) was visually observed to check for cracks or peeling.
○: No crack or peeling ×: Crack or peeling

<3> Initial haze (cloudiness value)
In accordance with JIS K7105 (6.4), the measurement was performed using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model HGM-2).

<4> Adhesion In accordance with JIS K5600 (5.9), using a razor blade, the hard coat film was cut into 11 vertical and horizontal cuts at 1 mm intervals to make 100 grids, After a well-registered trademark CT24 (manufactured by Nichiban Co., Ltd.) was peeled off, a peel test was performed to examine the ratio (x / 100) of the number of squares (x) remaining without peeling off the film.

<5> Scratch resistance In accordance with JIS K5600 (5.9), a Taber abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., model ROTARY ABRASION TESTER) and a wear ring (manufactured by TABER, trade name: CALIBRASE (registered trademark) CS-10F ) fitted with a, measuring the haze after 500 revolutions under a load 500 g (haze), we obtain a difference (haze difference) [Delta] H ₅₀₀ and haze before the test was evaluated. The haze was measured by the same method as in <3> above.

<6> Weather resistance Using an accelerated weather resistance tester using a metal halide lamp as a light source (trade name: KW-R5TP-A, manufactured by Daipura Wintes Co., Ltd.), the following three conditions of light irradiation, condensation, and darkness are repeated in order. After loading, the appearance and adhesion were evaluated in the same manner as in <2> and <4> above. The load was 50 cycles (600 hours) with light irradiation, condensation and darkness as one cycle, and a shower was performed for 10 seconds each before and after condensation.
-Light irradiation: Irradiation is performed for 4 hours under the conditions of an illuminance of 80 mW / cm ² (measured with an illuminance measuring device UIT-101 (model) manufactured by USHIO INC.), A black panel temperature of 63 ° C., and a relative humidity of 80%.
Condensation: Without irradiating light, the black panel temperature was naturally cooled from 63 ° C. to 30 ° C. under a relative humidity of 98% and held for 4 hours.
・ Dark: No light is irradiated and maintained for 4 hours under conditions of a black panel temperature of 75 ° C. and a relative humidity of 90%.

The above evaluation results are shown in Table 1 together with the type of each composition used and the corona discharge treatment conditions (discharge energy).

As is clear from Table 1, the samples of Examples 1 to 6 in which the primer layer was subjected to corona discharge treatment and subsequent silane coupling agent treatment had good initial appearance and hard coat film even after the accelerated weathering test. The adhesion of was maintained. On the other hand, in Example 7 where neither the corona discharge treatment nor the silane coupling agent treatment was performed, the hard coat film was completely peeled off by the accelerated weather resistance test, and only the silane coupling agent treatment was performed. Similarly, in Example 8, the hard coat film was completely peeled off. When observed with an optical microscope and FT-IR (ATR method), it was confirmed that the hard coat film was peeled off between the primer layer and the hard coat layer. From this result, performing both the corona discharge treatment and the silane coupling agent treatment prevents deterioration of the adhesion of the hard coat layer, and imparts scratch resistance, weather resistance, etc. to the resin substrate over a long period of time. Above, it is suggested to be extremely important.

The resin substrate having a hard coat film obtained according to the present invention has excellent scratch resistance and weather resistance, and is attached to a vehicle window material, a house, a building or the like that is attached to an automobile or various transportations. It is useful as a window material for building materials.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2010-283375 filed on Dec. 20, 2010 are incorporated herein as the disclosure of the present invention.

Claims

Applying a primer layer forming composition containing an acrylic polymer as a main component on at least one surface of a resin substrate and drying it to form a primer layer;
Applying corona discharge treatment to the surface of the primer layer;
A step of applying a silane coupling agent treatment by applying a silane coupling agent composition containing a silane coupling agent as a main component to the surface of the primer layer subjected to the corona discharge treatment, and drying;
A step of forming a hard coat layer by applying a composition for forming a hard coat layer containing organopolysiloxane as a main component to the surface of the primer layer that has been subjected to the corona discharge treatment and the silane coupling agent treatment, and then curing the composition. When,
The manufacturing method of the resin substrate which has a hard-coat film characterized by having.
The method for producing a resin substrate having a hard coat film according to claim 1, wherein the corona discharge treatment is a treatment in which the discharge energy on the surface of the primer layer is 20 W · min / m 2 to 500 W · min / m 2 .
The hard coat film according to claim 1 or 2, wherein the silane coupling agent contains a compound containing at least one selected from the group consisting of an epoxy group, a mercapto group, an isocyanate group, and a (meth) acryl group. Manufacturing method of resin substrate.
The silane coupling agent contains at least one selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane. The manufacturing method of the resin substrate which has a hard-coat film of description.
The organopolysiloxane contains silicon-containing bond units represented by the following T1 to T3 in the ratio of the number of the units: T1: T2: T3 = 0 to 5:15 to 40:55 to 85, and T3 / T2 = The ratio of the number of hydroxyl groups bonded to silicon atoms (B) to the number of alkoxy groups bonded to silicon atoms in the molecule (A) (B) / (A The method for producing a resin substrate having a hard coat film according to any one of claims 1 to 4, comprising an organopolysiloxane having a molecular average of 12.0 or more and a mass average molecular weight of 800 to 8000. .
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 an oxygen atom connecting silicon atoms.)
The method for producing a resin substrate having a hard coat film according to any one of claims 1 to 5, wherein the resin substrate is made of a polycarbonate resin.
A hard coat film comprising, on at least one surface of a resin substrate, a primer layer containing an acrylic polymer as a main component and a hard coat layer containing a cured product of organopolysiloxane as a main component in order from the resin substrate side A resin substrate having
A resin substrate having a hard coat film, wherein a corona discharge treatment and a silane coupling agent treatment are sequentially performed on the surface of the primer layer on the hard coat layer side.