JP2017114982A - Curable resin composition, laminate, and glasses - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide curable resin composition (light modulated resin composition) that can form a hard coat layer that expresses chromism.SOLUTION: A curable resin composition contains: inorganic fine particles with an average particle diameter of 0.01-10 μm; a chromic compound; at least one curable resin selected from the group consisting of thermosetting resin and active energy ray-curable resin; and a silicon-containing polymer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a curable resin composition for forming a hard coat layer, particularly a curable resin composition (also referred to as a light-modulating resin composition) capable of forming a hard coat layer having a chromic function.

  A substance that is colored in response to an external stimulus such as light, heat, electricity, etc., and fades and returns to its original state when the external stimulus is blocked is called a chromic substance. Typical applications of chromic materials include photochromic glass used for sunglasses and liquid crystals used for display panels of digital clocks and calculators.

In order to improve the responsiveness of the chromic substance, the film containing the chromic substance needs to have an appropriate flexibility. Therefore, conventionally, a hard coat layer or the like harder than that has been formed on the chromic film in order to ensure the durability of the product.
For example, as a photochromic lens used for sunglasses, there is a photochromic lens provided with a lens substrate, a photochromic film containing inorganic particles, a photochromic dye, and a resin component, and a functional film (hard coat film) (Patent Document 1, paragraph) 0011, 0013, 0022). The photochromic lens disclosed in Patent Document 1 includes a functional film (hard coat film) in order to ensure scratch resistance, wear resistance, and the like.

  The laminated body formed from a plurality of layers as described above is required to be configured with a smaller number of layers for reasons such as ease of production and reduction of processes.

JP2013-109254A

  Therefore, the present invention relates to a curable resin composition for forming a hard coat layer, which can form a hard coat layer exhibiting chromism (also referred to as a light-modulating resin composition). When the hard coat layer exhibits chromism, it is not necessary to provide a separate hard coat layer, and a product having a chromic function can be manufactured with a smaller number of layers.

  The present inventors have intensively studied to solve the above problems. As a result, it is a curable resin composition, and from a composition containing inorganic fine particles, a chromic compound, a curable resin, and a silicon-containing compound, it has been found that a layer expressing chromism can be formed while being a hard coat layer, The present invention has been completed.

The curable resin composition according to the first aspect of the present invention is composed of inorganic fine particles having an average particle diameter of 0.01 to 10 μm, a chromic compound, a thermosetting resin, and an active energy ray curable resin. At least one curable resin selected; and a silicon-containing polymer. The “average particle size” is the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.
If comprised in this way, the composition which can form the layer which expresses chromism although it is a hard-coat layer can be obtained. Therefore, a product that exhibits chromism can be manufactured with a smaller number of layers without providing a separate hard coat layer.

The curable resin composition according to the second aspect of the present invention is the curable resin composition according to the first aspect of the present invention, wherein the inorganic fine particles are added to the total solid content of the curable resin composition (cured). 10% by weight to 70% by weight based on the total amount of elements constituting the product).
If comprised in this way, the intensity | strength of the layer formed from the composition can be improved.

The curable resin composition according to a third aspect of the present invention is the curable resin composition according to the first aspect or the second aspect of the present invention, wherein the inorganic fine particles include silicon dioxide, zirconium dioxide, and oxidation. Tin, at least one particle selected from the group consisting of alumina, and an average particle diameter of 0.01 to 0.05 μm.
If comprised in this way, the intensity | strength of the layer formed from the composition can be improved more with an inorganic fine particle.

The curable resin composition according to the fourth aspect of the present invention is the curable resin composition according to any one of the first to third aspects of the present invention, wherein the chromic compound is a photochromic compound. is there.
If comprised in this way, the composition which can form the layer from which a color changes with irradiation of light can be obtained. Therefore, the layer formed from the composition is a sunglasses that is colored in places with strong sunlight, a window film for automobiles that has a function of cutting off the maturity energy of solar radiation and harmful UV rays, reducing the cooling load caused by solar radiation. Therefore, it can be applied to a window film for buildings that effectively shields sunlight entering from the window glass.

The curable resin composition according to the fifth aspect of the present invention is the curable resin composition according to the fourth aspect of the present invention, wherein the photochromic compound is a spiropyran compound, a spirooxazine compound, a naphthopyran compound, or a fulgimide compound. , A chromene compound and at least one compound selected from the group consisting of diarylethenes.
If comprised in this way, the composition containing the composition containing a compound suitable as a photochromic compound can be obtained.

The curable resin composition according to the sixth aspect of the present invention is the curable resin composition according to any one of the first to fifth aspects of the present invention, wherein the curable resin is active energy. It is a linear curable resin.
If comprised in this way, since the active energy ray curable resin has a quick curing rate, the manufacturing time of a hard-coat layer can be shortened. Furthermore, since it does not harden | cure unless it irradiates active energy ray curable resin, there are few restrictions of an application | coating process, and low temperature hardening is attained, and it is preferable.

The curable resin composition according to the seventh aspect of the present invention is the curable resin composition according to the sixth aspect of the present invention, wherein the active energy ray-curable resin is a (meth) acrylate monomer, unsaturated. It is at least one compound selected from the group consisting of a polyester resin, a polyester (meth) acrylate resin, an epoxy (meth) acrylate resin, and a urethane (meth) acrylate resin.
When configured in this manner, a resin having good curing reactivity and excellent workability can be used. Furthermore, by using these resins, a highly transparent cured film can be obtained.

The curable resin composition according to an eighth aspect of the present invention is the curable resin composition according to the seventh aspect of the present invention, wherein the active energy ray curable resin is a bifunctional or higher functional (meth) acryloyl. It is a urethane (meth) acrylate resin having a group.
If comprised in this way, resin which was especially excellent in intensity | strength and durability in addition to elongation rate and flexibility can be used.

The curable resin composition according to the ninth aspect of the present invention is the curable resin composition according to any one of the first to eighth aspects of the present invention, wherein the silicon-containing polymer is fluorine. Contains a silsesquioxane compound.
With this configuration, antifouling properties, non-adhesiveness, mold release properties, slipperiness, wear resistance, corrosion resistance, electrical insulation, antireflection properties, flame resistance, antistatic properties, chemical resistance, weather resistance A composition capable of forming a film having excellent properties can be obtained.

（上記式（１）中、Ｒ_ｆ ^１〜Ｒ_ｆ ^７はそれぞれ独立して、少なくとも１つのメチレンが酸素で置き換えられていてもよい炭素数１〜２０のフルオロアルキル、少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた炭素数６〜２０のフルオロアリール、または、アリール中の少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた炭素数７〜２０のフルオロアリールアルキルであり；
Ｌ^１は、−Ｙ^１−Ｏ−ＣＯ−（式中、Ｙ^１はＳｉと結合する、炭素数２〜１０のアルキレンである。）であり、かつ、Ｒ^１０は水素、炭素数１〜５のアルキルまたは炭素数６〜１０のアリールである；
またはＬ^１は、−Ｙ^２−Ｐｈ−（式中、Ｙ^２はＳｉと結合する、単結合または炭素数１〜１０のアルキレンであり、Ｐｈはフェニレンである。）であり、かつ、Ｒ^１０は水素である。）

（上記式（２）中、ｎは１〜１，０００の整数である；
Ｒ^１〜Ｒ^７が、それぞれ独立して水素、アルキル、アリールまたはアリールアルキルであり、これらのアルキル、アリールまたはアリールアルキルにおいて、少なくとも１つの水素がフッ素で置き換えられてもよく、そして少なくとも１つのメチレンが酸素またはシクロアルキレンで置き換えられてもよく；
Ｌ^２は、−Ｙ^１−Ｏ−ＣＯ−（式中、Ｙ^１はＳｉと結合する、炭素数２〜１０のアルキレンである。）であり、かつ、Ｒ^２０は水素、直鎖もしくは分岐鎖の炭素数１〜５のアルキルまたは炭素数６〜１０のアリールである；
Ｌ^２は、−Ｘ^１−Ｙ_ｐ−Ｏ−ＣＯ−（式中、Ｘ^１はＳｉと結合する、炭素数２〜２０のアルキレンであり、Ｙ_ｐは−ＯＣＨ_２ＣＨ_２−、−ＯＣＨＣＨ_３ＣＨ_２−または−ＯＣＨ_２ＣＨ（ＣＨ_３）−であり、ｐは０〜３の整数である。）であり、かつ、Ｒ^２０は水素、炭素数１〜５のアルキルまたは炭素数６〜１０のアリールである；または
Ｌ^２は、−Ｙ^２−Ｐｈ−（式中、Ｙ^２はＳｉと結合する、単結合または炭素数１〜１０のアルキレンであり、Ｐｈはフェニレンである。）であり、かつ、Ｒ^２０は水素である。）
このように構成すると、汚防性、非粘着性、離型性、滑り性、耐磨耗性、耐蝕性、電気絶縁性、反射防止特性、難燃性、帯電防止特性、耐薬品性、耐候性などに優れ、さらに両親媒性、クリーニング性を有する膜を形成可能な組成物を得ることができる。 The curable resin composition according to the tenth aspect of the present invention is the curable resin composition according to any one of the first to ninth aspects of the present invention, wherein the silicon-containing polymer is: It is a polymer containing the structural unit 1 represented by the formula (1) and further comprising the structural unit 2 represented by the following formula (2).

(In the above formula (1), R _f ^{1 to} R _f ⁷ are each independently fluoroalkyl having 1 to 20 carbon atoms in which at least one methylene may be replaced by oxygen, and at least one hydrogen is fluorine or C6-C20 fluoroaryl substituted with trifluoromethyl or C7-C20 fluoroarylalkyl in which at least one hydrogen in aryl is replaced with fluorine or trifluoromethyl;
L ¹ is —Y ¹ —O—CO— (wherein Y ¹ is an alkylene having 2 to 10 carbon atoms bonded to Si), and R ¹⁰ is hydrogen or 1 to 5 carbon atoms. Alkyl or aryl having 6 to 10 carbon atoms;
Or L ¹ is —Y ² —Ph— (wherein Y ² is a single bond or alkylene having 1 to 10 carbon atoms bonded to Si, and Ph is phenylene), and R ¹⁰ Is hydrogen. )

(In the above formula (2), n is an integer of 1 to 1,000;
R ^{1 to} R ⁷ are each independently hydrogen, alkyl, aryl or arylalkyl, in which at least one hydrogen may be replaced by fluorine, and at least one methylene May be replaced by oxygen or cycloalkylene;
L ² is —Y ¹ —O—CO— (wherein Y ¹ is an alkylene having 2 to 10 carbon atoms bonded to Si), and R ²⁰ is hydrogen, linear or branched. Or an alkyl having 1 to 5 carbon atoms or an aryl having 6 to 10 carbon atoms;
L ² is —X ¹ —Y _p —O—CO— (wherein X ¹ is an alkylene having 2 to 20 carbon atoms bonded to Si, and Y _p is —OCH ₂ CH ₂ —, —OCHCH _3. CH ₂ — or —OCH ₂ CH (CH ₃ ) —, p is an integer of 0 to 3), and R ²⁰ is hydrogen, alkyl having 1 to 5 carbons, or 6 to 10 carbons. Or L ² is -Y ² -Ph- (wherein Y ² is a single bond or alkylene having 1 to 10 carbon atoms bonded to Si, and Ph is phenylene). And R ²⁰ is hydrogen. )
With this configuration, antifouling properties, non-adhesiveness, mold release properties, slipperiness, wear resistance, corrosion resistance, electrical insulation, antireflection properties, flame resistance, antistatic properties, chemical resistance, weather resistance The composition which can form the film | membrane which is excellent in property etc., and also has an amphiphilic property and a cleaning property can be obtained.

The curable resin composition according to an eleventh aspect of the present invention further includes an organic solvent in the curable resin composition according to any one of the first to tenth aspects of the present invention, The organic solvent is at least one solvent selected from the group consisting of aromatic and aliphatic hydrocarbons, ethers, esters, alcohols, and ketones.
If comprised in this way, it can make it easy to apply | coat curable resin composition as a coating liquid.

The laminate according to the twelfth aspect of the present invention comprises, for example, as shown in FIG. 1 or FIG. 2, a base material 2; and curing according to any one of the first to eleventh aspects of the present invention. A hard coat layer 1 obtained by curing the conductive resin composition.
If comprised in this way, the intensity | strength of a laminated body can be improved with a hard-coat layer. Moreover, since a hard-coat layer expresses chromism, the laminated body which has intensity | strength can be applied to various chromism products.

The laminate according to a thirteenth aspect of the present invention is the laminate according to the twelfth aspect of the present invention, wherein the base material is glass, plastic, metal, or ceramics.
If comprised in this way, a laminated body can be applied to various chromism products by selection of a suitable base material.

The laminate according to the fourteenth aspect of the present invention is the laminate according to the twelfth or thirteenth aspect of the present invention, wherein the plastic is polyethylene terephthalate (PET), polycarbonate, nylon, or allyl diglycol carbonate. It is.
If comprised in this way, a laminated body can be applied to various chromism products by selection of an appropriate material.

The eyeglasses according to a fifteenth aspect of the present invention includes: a lens made of the laminate according to any one of the first to fourteenth aspects of the present invention; and a frame that holds the lens.
If comprised in this way, the spectacles provided with the lens which has the outstanding intensity | strength and shielding rate can be obtained.

  The curable resin composition of the present invention is a curable resin composition capable of forming a hard coat layer, and further a curable resin composition capable of forming a hard coat layer expressing chromism. Therefore, when the curable resin composition of the present invention is used, a product exhibiting chromism can be produced with a smaller number of layers without separately providing a hard coat layer.

2 is a cross-sectional view illustrating a layer configuration of a laminated body 10. FIG. 3 is a cross-sectional view illustrating a layer configuration of a stacked body 20. FIG. It is a graph which shows the relationship between the shielding rate of Examples 11-15, and content of an inorganic fine particle. It is a graph which shows the relationship between the shielding rate of Examples 16-17, and content of an inorganic fine particle. It is a graph which shows the relationship between the shielding rate of Comparative Examples 11, 13, and 14 and the content of inorganic fine particles. It is a graph which shows the relationship between the shielding rate of Example 18, and content of an inorganic fine particle.

  Embodiments of the present invention will be described below with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same or similar reference numerals, and redundant description is omitted. Further, the present invention is not limited to the following embodiments.

[Curable resin composition]
The curable resin composition (also referred to as a light-modulating resin composition) according to the first embodiment of the present invention includes inorganic fine particles, a chromic compound, a curable resin, and a silicon-containing polymer. The curable resin composition may further contain a solvent and an additive.

[Inorganic fine particles]
Examples of the inorganic fine particles include inorganic oxide fine particles because they are excellent in dispersibility and easily available. For example, aluminum oxide (alumina), silicon dioxide, titanium oxide, tin oxide, zirconium dioxide, magnesium fluoride, cerium oxide, copper oxide, zinc oxide, apatite, fluorite, silica glass, iron oxide, antimony oxide, cryolite Calcite, gypsum, layered silicate minerals, and talc. These may be used alone or in combination of two or more. Among these, silicon dioxide (silica), zirconium dioxide, tin oxide, alumina, cerium oxide, zinc oxide, and the like are preferable, and silicon dioxide, zirconium dioxide, tin oxide, and alumina are particularly preferable.
When silicon dioxide, zirconium dioxide, tin oxide, or alumina is used, the strength of the cured film can be further improved. Furthermore, when silicon dioxide is used, the cured film can have a low refractive index. When zirconium dioxide or tin oxide is used, the cured film can have a high refractive index. If the refractive index of the film can be adjusted, for example, by combining it with the refractive index of the substrate, interference fringes can be suppressed and the appearance of the cured film can be improved. Further, by providing a low refractive index film on the high refractive index film, an antireflection function can be provided.

The average particle diameter of the inorganic fine particles is preferably from 0.01 to 10 μm, more preferably from 0.01 to 1 μm, particularly preferably from 0.01 to 0.05 μm.
An average particle size of 0.01 to 10 μm is preferable because a photochromic lens having transparency suitable as a spectacle lens can be obtained. Furthermore, it is preferable that the average particle size is 0.01 μm or more because the dispersibility in the resin is improved and the strength of the formed layer is increased. Since it is excellent in transparency as it is 10 micrometers or less, it is preferable. It is especially preferable that it is 0.01-0.05 micrometer from a viewpoint of making hardness and transparency compatible.

The inorganic fine particles are preferably contained in an amount of 10 to 70% by weight, more preferably 10 to 60% by weight, particularly preferably 20 to 60% by weight based on the total solid content of the curable resin composition.
When the content of the inorganic fine particles is 10% by weight or more, the hardness as the hard coat layer can be satisfied. Moreover, the function of chromism expression of a chromic material can be effectively increased as it is 10 weight% or more. For example, as shown in the Examples, when a photochromic material is used, there is an effect of increasing the shielding rate even with the same addition amount, and the amount of expensive chromic material used can be reduced to the limit. When the content is 70% by weight or less, a transparent film maintaining film forming properties can be obtained.

The inorganic fine particles may be added to the curable resin composition in a dry state, or may be added to the curable resin composition in a state dispersed in an appropriate solvent. Addition in the state of being dispersed in a solvent is preferable because it can be stably dispersed uniformly throughout the curable resin composition.
In particular, the inorganic fine particles are preferably added to the curable resin composition in the state of a colloidal solution in which the inorganic fine particles are dispersed. Among these, it is preferable to add the inorganic fine particles to the curable resin composition in the state of a colloidal solution using an organic solvent or a monomer as a dispersion medium. The inorganic fine particles contained in such a colloidal solution have a surface that has been hydrophobized by a surface modification treatment with silicon, etc., so that they have excellent affinity with curable components and are uniformly dispersed in the curable resin composition. This is possible.
Examples of the dispersion medium include ether solvents such as propylene glycol monomethyl ether, ketone solvents such as methyl ethyl ketone, acrylic monomers such as tripropylene glycol diacrylate and hexanediol diacrylate, ester solvents such as methoxypropyl acetate, and methoxypropanol. Examples thereof include organic solvents such as alcohol solvents. The concentration of the inorganic fine particles in the dispersion is, for example, about 20 to 50% by weight, but is not particularly limited.

[Chromic compound]
An example of the chromic compound is a photochromic compound. Alternatively, it may be a thermochromic compound or an electrochromic compound. Alternatively, a mixture thereof may be used.
A well-known thing can be used as a photochromic compound, a thermochromic compound, and an electrochromic compound. For example, examples of the photochromic compound include a spiropyran compound, a spirooxazine compound, a naphthopyran compound, a fulgimide compound, a chromene compound, a diarylethene, an azobenzene compound, and a mixture thereof. Examples of thermochromic compounds include salicylidene aniline compounds, triphenylmethane compounds, spiropyran compounds, and mixtures thereof. Electrochromic compounds include tungsten oxide, iridium oxide, and Prussian blue for inorganic systems, viologen compounds for organic systems, polythiophene, polyaniline that can be synthesized by electrochemical or chemical oxidation of aniline, and rare earth diphthalocyanine as a metal complex. And mixtures thereof.

  The chromic compound is not particularly limited, but may include 0.01 to 20% by weight, 0.1 to 15% by weight, or 0% based on the total solid content of the curable resin composition. It may be 1 to 10% by weight. When the content of the chromic compound is 0.01% by weight or more, a color density necessary for sunglasses can be obtained, and when it is 20% by weight or less, the raw material cost can be suppressed. However, the addition amount may be an amount required to exhibit its function depending on the application. For example, in the case of a photochromic dye, there are many substances that are effective even at 10% by weight or less depending on the application.

[Curable resin]
As the curable resin, a thermosetting resin or an active energy ray curable resin can be used, and an active energy ray curable resin can be preferably used. These may be used alone or in combination of two or more. The content of the curable resin is 30 to 90% by weight, preferably 40 to 90% by weight, and particularly preferably 40 to 80% by weight with respect to the total solid content of the curable resin composition. When the content is in the range of 30 to 90% by weight, a transparent resin film can be formed.

-Thermosetting resin As a thermosetting resin, a melamine resin, a urethane resin, an epoxy resin, a silicone resin etc. can be utilized. Examples of the melamine resin include alkylated melamine resins such as methylated melamine resins and butylated melamine resins, methylol-type melamine resins, and imino-type melamine resins. Examples of the urethane resin include polyether type polyurethane resin, polyester type polyurethane resin, polycarbonate type polyurethane resin, and polyester polycarbonate type polyurethane resin. Examples of the epoxy resin include a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a polymer of a monomer having an oxirane, or a copolymer of a monomer having an oxirane and another monomer. . Examples of the silicone resin include methyl silicone resin, methylphenyl silicone resin, and modified silicone resin. Examples of the modified silicone resin include alkyd modification, epoxy modification, acrylic modification, and polyester modification. These may be used alone or in combination of two or more.

  When using a thermosetting resin, you may add a hardening | curing agent as needed. In this case, the content of the curing agent is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight with respect to the total solid content of the thermosetting resin composition, and 0.1 to 5% by weight. A weight of 4 is particularly preferred. As the curing agent, an isocyanate, a carboxylic acid, an amine, an acid anhydride compound, an acid generator, a double salt that is an onium salt that releases a Lewis acid or a derivative thereof can be used, and preferably an onium salt that releases a Lewis acid. A certain double salt or a derivative thereof can be used. In addition, when isocyanate is used as a hardening | curing agent, the thermosetting reaction with a polyol can be utilized by a well-known method.

Active energy ray curable resin Active energy ray curable resin includes radicals such as (meth) acrylate monomer, unsaturated polyester resin, polyester (meth) acrylate resin, epoxy (meth) acrylate resin, urethane (meth) acrylate resin Resins having an unsaturated bond that can be polymerized can be used.

  Examples of the (meth) acrylate monomer include compounds obtained by reacting an alcohol with an α, β-unsaturated carboxylic acid. For example, polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (Meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetra Methylolmethane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Moreover, the compound which has a silsesquioxane skeleton and has a (meth) acrylate in a functional group is also mentioned.

The unsaturated polyester resin is obtained by dissolving a condensation product (unsaturated polyester) in an esterification reaction between an alcohol and an unsaturated polybasic acid (and a saturated polybasic acid if necessary) in a polymerizable monomer. Can be mentioned.
The unsaturated polyester resin can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid or its anhydride is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane -Alcohol such as 1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A is reacted as an alcohol component, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthal Acid, adipic acid, sebacic acid, etc. Polybasic acids or anhydrides thereof polymerizable not have an unsaturated bond may include those prepared by adding as an acid component.

The polyester (meth) acrylate resin includes (1) an epoxy compound containing an α, β-unsaturated carboxylic acid ester in a terminal carboxyl polyester obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and an alcohol. (Meth) acrylate obtained by reaction, (2) (meth) acrylate obtained by reacting a hydroxyl group-containing acrylate with polyester of terminal carboxyl obtained from saturated polybasic acid and / or unsaturated polybasic acid and alcohol, 3) (Meth) acrylates obtained by reacting (meth) acrylic acid with polyesters having terminal hydroxyl groups obtained from saturated polybasic acids and / or unsaturated polybasic acids and alcohols.
Polybasic acids that do not have polymerizable unsaturated bonds such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid are used as raw materials for polyester (meth) acrylate. Or an anhydride thereof, and examples of the polymerizable unsaturated polybasic acid include polybasic acids having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid, or anhydrides thereof. Furthermore, as an alcohol component, it is the same as that of the said unsaturated polyester.

  Examples of the epoxy (meth) acrylate resin include a compound having a polymerizable unsaturated bond (vinyl) formed by a ring-opening reaction between a compound having glycidyl and a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. An ester) is dissolved in a polymerizable monomer. The vinyl ester is produced by a known method, and examples thereof include epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid. Further, various epoxy resins may be reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.) to impart flexibility. Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolak glycidyl ethers, and the like.

As the urethane (meth) acrylate resin, for example, after reacting a polyisocyanate with a polyhydroxy compound or an alcohol, a hydroxyl group-containing (meth) acryl compound and, if necessary, a hydroxyl group-containing allyl ether compound are reacted. And a radically polymerizable unsaturated group-containing oligomer that can be obtained by:
Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, Phenylmethane triisocyanate, Bannock D-750, Crisbon NK (trade name; manufactured by Dainippon Ink & Chemicals, Inc.), Desmodur L (trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Japan) Polyurethane Industry Co., Ltd.), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), and the like.
Examples of the polyhydroxy compound include polyester polyol, polyether polyol, and the like. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, Trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide Adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethyl N'okishido - propylene oxide adduct and the like.
Specific examples of the alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butanediol. , Adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane Examples include glycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, and 2,7-decalin glycol.
Although it does not specifically limit as said hydroxyl-containing (meth) acryl compound, A hydroxyl-containing (meth) acrylic acid ester is preferable, Specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanursannodi (meth) acrylate, pentaesitol tri (meth) ) Acrylate and the like.

  Active energy ray-curable resin fats include (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins, or mixtures thereof. preferable. More preferably, it is a urethane (meth) acrylate resin having a bifunctional or higher functional (meth) acryloyl group. These resins are preferable because they have good curing reactivity and excellent processability. Furthermore, by using these resins, a highly transparent cured film can be obtained. In addition, these resins are preferable because a curing method using UV curing can be used, so that the curing time can be shortened and the resin is suitable for processing by roll-to-roll or processing using a conveyor device.

  When using an active energy ray-curable resin, a curing agent may be added as necessary. In this case, the content of the curing agent is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and more preferably 0.1 to 4% with respect to the total solid content of the curable resin composition. Weight is particularly preferred. An active energy ray polymerization initiator can be used as the curing agent. The active energy ray polymerization initiator is not particularly limited as long as it is a compound that generates radicals upon irradiation with active energy rays such as ultraviolet rays and visible rays. Examples of the compound used as the active energy ray polymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2 -Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropa -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, ethyl 1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di ( t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bi (Trichloromethyl) -s-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] -2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5 (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis ( 7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazo 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2 , 4-Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η5- , 4-cyclopentadiene-1-yl) - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) - phenyl) titanium, and the like. These compounds may be used alone or in combination of two or more. 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxy) Carbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone is preferred.

[Silicon-containing polymer]
A silicon-containing polymer is a polymer containing silicon in its structure. An example of the silicon-containing polymer is a fluorine silsesquioxane compound.
Hereinafter, the silicon-containing polymer will be described in detail. The following silicon-containing polymer can be synthesized by a known method. For example, a synthesis method is described in Japanese Patent No. 5418224.

The polymer of the present invention comprises a fluorosilsesquioxane-derived structural unit 1 having an addition-polymerizable functional group, or a fluorosilsesquioxane-derived structural unit 1 having an addition-polymerizable functional group and an addition-polymerizable functional group. It is a polymer which has the structural unit 2 derived from the organopolysiloxane which has.
The polymer of the present invention may be an ordered polymer such as block copolymer or a random polymer, but is preferably a random polymer. Further, the polymer of the present invention may have a crosslinked structure or a graft polymer.

When the polymer of the present invention comprises the structural unit 1 and the structural unit 2, the molar ratio between the structural unit 1 and the structural unit 2 may be appropriately determined according to the target polymer, but is 0.001: 99. It is preferably 999 to about 99.999: 0.001, more preferably 0.1: 99.9 to 99.9: 0.1.
Further, when the polymer of the present invention includes the structural unit 3 or the structural unit 4 which is an arbitrary structural unit, the molar ratio of the structural unit 1 to the arbitrary structural unit is about 0.001: 99.999 to about 99.999: 0.001 is preferable, and similarly, the molar ratio of the structural unit 2 to an arbitrary structural unit is about 0.001: 99.999 to about 99.999: 0.001. preferable.
Moreover, although the weight average molecular weight of a copolymer changes with the structures and the content rate of the structural unit 1 and the structural unit 2, it is preferable that it is about 1000-1 million. The molecular weight distribution (Mw / Mn) of the polymer of the present invention is not particularly limited, but is usually about 1.01 to 2.5.
Moreover, it is preferable that the fluorine atom content rate contained in the polymer of this invention is 0.001-65 weight%.

フルオロシルセスキオキサン由来の構成単位１は、上記式（１）で示される構成を有せば特に限定されない。式（１）中、Ｒ_ｆ ^１〜Ｒ_ｆ ^７がそれぞれ独立して、少なくとも１つのメチレンが酸素で置き換えられていてもよい直鎖状もしくは分岐鎖状の炭素数１〜２０のフルオロアルキル、少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた炭素数６〜２０のフルオロアリール、または、アリール中の少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた炭素数７〜２０のフルオロアリールアルキルであり；
Ｌ^１は、−Ｙ^１−Ｏ−ＣＯ−（式中、Ｙ^１はフルオロシルセスキオキサン骨格を構成するＳｉと結合する、炭素数２〜１０のアルキレンである。）であり、かつ、Ｒ^１０は水素、炭素数１〜５のアルキルまたは炭素数６〜１０のアリールである；
またはＬ^１は、−Ｙ^２−Ｐｈ−（式中、Ｙ^２はフルオロシルセスキオキサン骨格を構成するＳｉと結合する、単結合または炭素数１〜１０のアルキレンであり、Ｐｈはフェニレンである。）であり、かつ、Ｒ^１０は水素である。
式（１）中、Ｒ_ｆ ^１〜Ｒ_ｆ ^７の全てが、フルオロアルキル、フルオロアリールまたはフルオロアリールアルキルであることが好ましい。ここで、Ｒ_ｆ ^１〜Ｒ_ｆ ^７におけるフルオロアルキルは直鎖状もしくは分岐鎖状のフルオロアルキルのどちらでもよい。 ・ Structural unit 1 derived from fluorosilsesquioxane

The structural unit 1 derived from fluorosilsesquioxane is not particularly limited as long as it has the structure represented by the above formula (1). In formula (1), R _f ^{1 to} R _f ⁷ are each independently a linear or branched fluoroalkyl having 1 to 20 carbon atoms in which at least one methylene may be replaced by oxygen, Fluoroaryl having 6 to 20 carbon atoms in which one hydrogen is replaced with fluorine or trifluoromethyl, or Fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in aryl is replaced with fluorine or trifluoromethyl Is;
L ¹ is —Y ¹ —O—CO— (wherein Y ¹ is an alkylene having 2 to 10 carbon atoms bonded to Si constituting the fluorosilsesquioxane skeleton), and R 1 ¹⁰ is hydrogen, alkyl having 1 to 5 carbons or aryl having 6 to 10 carbons;
Alternatively, L ¹ represents —Y ² —Ph— (wherein Y ² is a single bond or alkylene having 1 to 10 carbon atoms bonded to Si constituting the fluorosilsesquioxane skeleton, and Ph is phenylene. And R ¹⁰ is hydrogen.
In formula (1), it is preferable that all of R _f ^{1 to} R _f ⁷ are fluoroalkyl, fluoroaryl or fluoroarylalkyl. Here, the fluoroalkyl in R _f ^{1 to} R _f ⁷ may be either a linear or branched fluoroalkyl.

Here, the carbon number of the fluoroalkyl in _R ^f 1 _{to R} ^{f 7} in the formula (1) is 1 to 20, preferably from 3 to 14. Furthermore, at least one methylene of the fluoroalkyl may be replaced with oxygen. Here, methylene includes —CH ₂ —, —CFH— or —CF ₂ —. That is, “at least one methylene may be replaced with oxygen” means that —CH ₂ —, —CFH—, or —CF ₂ — may be replaced with —O—. However, in fluoroalkyl, two oxygens are not bonded (—O—O—). Also, in the preferred fluoroalkyl, the methylene adjacent to Si is not replaced with oxygen, and the end opposite to Si is CF ₃ . Furthermore, it is preferable that —CF ₂ — be replaced with oxygen rather than —CH ₂ — or —CFH— to be replaced with oxygen. Preferred specific examples of such fluoroalkyl include 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrododecyl, henicosafluoro-1,1,2,2-tetrahydro Dodecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl and the like are included. Among these, perfluoroalkylethyl is preferably exemplified.

The fluoroaryl in R _f ^{1 to} R _f ⁷ is one in which at least one or two or more hydrogens in aryl are replaced with fluorine or trifluoromethyl, and the number of carbon atoms is 6 to 20 Is preferable, and 6 is more preferable. Examples of such aryl include phenyl, naphthyl and the like, as well as heteroaryl. Specific examples include fluorophenyl such as pentafluorophenyl and trifluoromethylphenyl.

The fluoroarylalkyl in R _f ^{1 to} R _f ⁷ is an alkyl containing an aryl containing fluorine, and preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. The fluorine contained is preferably one in which at least one hydrogen in aryl is replaced by fluorine or trifluoromethyl. Examples of the aryl moiety include phenyl, naphthyl and the like, as well as heteroaryl, and examples of the alkyl moiety include methyl, ethyl, propyl and the like.

R _f ^{1 to} R _f ⁷ are preferably fluoroalkyl among fluoroalkyl, fluoroaryl and fluoroarylalkyl. Of the fluoroalkyls, perfluoroalkylethyl is preferred, more preferably 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl or tri Decafluoro-1,1,2,2-tetrahydrooctyl.

また、式（１）において、Ｌ^１は上記式（５）または（７）で表される基であることが好ましい。
式（５）においてＹ^１は、炭素数２〜１０のアルキレンであり、好ましくは炭素数２〜６のアルキレンであり、さらに好ましくはプロピレンである。但し、式（５）の基の両端を構成するＹ^１とカルボニルにおいて、Ｙ^１がフルオロシルセスキオキサン骨格を構成するＳｉと結合し、かつ、カルボニルがＣと結合する。
式（７）において、Ｙ^２は、単結合または炭素数２〜１０のアルキレンであり、好ましくは単結合または炭素数２〜６のアルキレンであり、より好ましくは単結合または炭素数１あるいは２のアルキレンであり、特に好ましくは単結合またはエチレンである。またメチレンは、ベンゼン環のいずれかの炭素に結合しており、好ましくはＹ^２に対してパラ位の炭素に結合している。但し、式（７）の基の両端を構成するＹ^２とフェニルにおいて、Ｙ^２がフルオロシルセスキオキサン骨格を構成するＳｉと結合し、かつ、フェニルがＣと結合する。

In Formula (1), L ¹ is preferably a group represented by Formula (5) or (7).
In Formula (5), Y ¹ is alkylene having 2 to 10 carbons, preferably alkylene having 2 to 6 carbons, and more preferably propylene. However, in Y ¹ and carbonyl constituting both ends of the group of the formula (5), Y ¹ is bonded to Si constituting the fluorosilsesquioxane skeleton, and carbonyl is bonded to C.
In Formula (7), Y ² is a single bond or alkylene having 2 to 10 carbon atoms, preferably a single bond or alkylene having 2 to 6 carbon atoms, more preferably a single bond or having 1 or 2 carbon atoms. Alkylene, particularly preferably a single bond or ethylene. Methylene is bonded to any carbon of the benzene ring, and preferably bonded to carbon in the para position with respect to Y ² . However, in Y ² and phenyl constituting both ends of the group of the formula (7), Y ² is bonded to Si forming the fluorosilsesquioxane skeleton, and phenyl is bonded to C.

オルガノポリシロキサン由来の構成単位２は、上記式（２）で示される構成を有せば特に限定されない。式（２）中、ｎは１〜１，０００の整数である；Ｒ^１〜Ｒ^７が、それぞれ独立して水素、アルキル、アリールまたはアリールアルキルであり、これらのアルキル、アリールまたはアリールアルキルにおいて、少なくとも１つの水素がフッ素で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−が−Ｏ−またはシクロアルキレンで置き換えられてもよく；Ｌ^２は、−Ｙ^１−Ｏ−ＣＯ−（式中、Ｙ^１はオルガノポリシロキサン骨格を構成するＳｉと結合する、炭素数２〜１０のアルキレンである。）であり、かつ、Ｒ^２０は水素、直鎖もしくは分岐鎖の炭素数１〜５のアルキルまたは炭素数６〜１０のアリールである；
Ｌ^２は、−Ｘ^１−Ｙ_ｐ−Ｏ−ＣＯ−（式中、Ｘ^１はオルガノポリシロキサン骨格を構成するＳｉと結合する、炭素数２〜２０のアルキレンであり、Ｙ_ｐは−ＯＣＨ_２ＣＨ_２−、−ＯＣＨＣＨ_３ＣＨ_２−または−ＯＣＨ_２ＣＨ（ＣＨ_３）−であり、ｐは０〜３の整数である。）であり、かつ、Ｒ^２０は水素、炭素数１〜５のアルキルまたは炭素数６〜１０のアリールである；または
Ｌ^２は、−Ｙ^２−Ｐｈ−（式中、Ｙ^２はオルガノポリシロキサン骨格を構成するＳｉと結合する、単結合または炭素数１〜１０のアルキレンであり、Ｐｈはフェニレンである。）であり、かつ、Ｒ^２０は水素であり；
式（２）におけるＲ^１、Ｒ^２、Ｒ^５、Ｒ^６およびＲ^７がそれぞれ独立して少なくとも１つの水素がフッ素で置き換えられてもよいアルキル、少なくとも１つの水素がフッ素で置き換えられてもよいアリール、または、少なくとも１つの水素がフッ素で置き換えられてもよいアリールアルキル；Ｒ^３およびＲ^４が、それぞれ独立して水素、フェニルまたは少なくとも１つの水素がフッ素で置き換えられてもよいアルキルが好ましい。より好ましくは、Ｒ^１、Ｒ^２、Ｒ^５およびＲ^６がそれぞれ独立してメチルまたはフェニルであり；
Ｒ^３およびＲ^４がそれぞれ独立してメチル、フェニルまたは３，３，３−トリフルオロプロピルであり；
Ｒ^７がメチル、エチル、プロピル、ブチル、イソブチル、フェニル、３，３，３−トリフルオロプロピル、３，３，４，４，４−ペンタフルオロブチル、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル、トリデカフルオロ−１，１，２，２−テトラヒドロオクチル、ヘプタデカフルオロ−１，１，２，２−テトラヒドロデシル、ヘンイコサフルオロ−１，１，２，２−テトラヒドロドデシル、ペンタコサフルオロ−１，１，２，２−テトラヒドロテトラデシル、（３−ヘプタフルオロイソプロポキシ）プロピル、ペンタフルオロフェニルプロピル、ペンタフルオロフェニル、またはα，α，α−トリフルオロメチルフェニルである。 ・ Structural unit 2 derived from organopolysiloxane
The polymer of the present invention may contain a structural unit 2 derived from an organopolysiloxane typified by polydimethylsiloxane, in addition to the structural unit 1 described above. When the organopolysiloxane is grafted to the side chain of the organic polymer, the resulting polymer has unique characteristics as an organopolysiloxane, such as water repellency, releasability, slipperiness, low friction, antithrombogenicity, and heat resistance. It is possible to develop electrical characteristics, flexibility, oxygen permeability, and radiation resistance.

The structural unit 2 derived from organopolysiloxane is not particularly limited as long as it has the structure represented by the above formula (2). In the formula (2), n is an integer of ^{1 to} 1,000; R ^{1 to} R ⁷ are each independently hydrogen, alkyl, aryl or arylalkyl, and in these alkyl, aryl or arylalkyl, At least one hydrogen may be replaced with fluorine, and at least one —CH ₂ — may be replaced with —O— or cycloalkylene; L ² represents —Y ¹ —O—CO— (wherein Y ¹ is an alkylene having 2 to 10 carbon atoms bonded to Si constituting the organopolysiloxane skeleton), and R ²⁰ is hydrogen, a linear or branched alkyl having 1 to 5 carbon atoms. Or aryl having 6 to 10 carbon atoms;
L ² is —X ¹ —Y _p —O—CO— (wherein X ¹ is an alkylene having 2 to 20 carbon atoms bonded to Si constituting the organopolysiloxane skeleton, and Y _p is —OCH _2. CH ₂ —, —OCHCH ₃ CH ₂ — or —OCH ₂ CH (CH ₃ ) —, and p is an integer of 0 to 3), and R ²⁰ is hydrogen and has 1 to 5 carbon atoms. Alkyl or aryl having 6 to 10 carbon atoms; or L ² is —Y ² —Ph— (wherein Y ² is bonded to Si constituting the organopolysiloxane skeleton, or a single bond or 1 to 10 carbon atoms) And Ph is phenylene), and R ²⁰ is hydrogen;
R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ in formula (2) are each independently an alkyl in which at least one hydrogen may be replaced with fluorine, and at least one hydrogen may be replaced with fluorine Preference is given to aryl or arylalkyl in which at least one hydrogen may be replaced by fluorine; R ³ and R ⁴ are each independently hydrogen, phenyl or alkyl in which at least one hydrogen can be replaced by fluorine. More preferably, R ¹ , R ² , R ⁵ and R ⁶ are each independently methyl or phenyl;
R ³ and R ⁴ are each independently methyl, phenyl or 3,3,3-trifluoropropyl;
R ⁷ is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5 , 6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1, 2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α, α-tri Fluoromethylphenyl.

ここで、式（２）において、Ｌ^２は上記式（５）、（６）または（７）で表される基であることが好ましい。
式（５）と式（７）は、式（１）のＬ^１と同様である。
式（６）において、Ｘ^１は炭素数１〜２０のアルキレンであり、好ましくは−ＣＨ_２ＣＨ_２ＣＨ_２−であり；Ｙ_ｐは−ＯＣＨ_２ＣＨ_２−、−ＯＣＨ（ＣＨ_３）ＣＨ_２−または−ＯＣＨ_２ＣＨ（ＣＨ_３）−であり、好ましくは−ＯＣＨ_２ＣＨ_２−であり；ｐは０〜３の整数であり、好ましくは０または１である。但し、式（６）の基の両端を構成するＸ^１とカルボニルにおいて、Ｘ^１がフルオロシルセスキオキサン骨格を構成するＳｉと結合し、かつ、カルボニルがＣと結合する。

Here, in the formula (2), L ² is preferably a group represented by the formula (5), (6) or (7).
Expressions (5) and (7) are the same as L ^{1 in} Expression (1).
In the formula (6), X ¹ is alkylene having 1 to 20 carbons, preferably —CH ₂ CH ₂ CH ₂ —; Y _p is —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH _2. - or -OCH ₂ CH (CH ₃₎ - and is, preferably -OCH ₂ CH ₂ - and it; p is an integer of 0 to 3, preferably 0 or 1. However, in X ¹ and carbonyl constituting both ends of the group of the formula (6), X ¹ is bonded to Si constituting the fluorosilsesquioxane skeleton, and carbonyl is bonded to C.

（１）構成単位３
構成単位３は、上記式（３）で示される構成を有せば特に限定されない。式（３）中、Ｒ^３１が水素、炭素数１〜３０のアルキル、炭素数６〜３０のアリールまたは炭素数７〜４０のアリールアルキルであり、これらのアルキル、アリールまたはアリールアルキルにおいて、少なくとも１つの水素がフッ素で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−が−Ｏ−またはシクロアルキレンで置き換えられてもよく；
Ｒ^３２が架橋性または非架橋性の基より選択される基である。
好ましくは、Ｒ^３１が水素、炭素数１〜１０のアルキル、炭素数６〜１０のアリールまたは炭素数７〜２０のアリールアルキルであり、これらのアルキル、アリールまたはアリールアルキルにおいて、少なくとも１つの水素がフッ素で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−が−Ｏ−で置き換えられてもよい。
好ましくは、Ｒ^３２がヒドロキシル、環状エーテルを含む一価の官能基、ハロゲン化アルキル、ブロックドイソシアネート、イソシアネート、アミノ及びカルボキシルから選択される基を有する基、水素、炭素数１〜１２のアルキル、炭素数６〜１０のアリールまたは炭素数７〜２０のアリールアルキルであり、これらのアルキル、アリールまたはアリールアルキルにおいて、少なくとも１つの水素がフッ素で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−が−Ｏ−で置き換えられてもよい。
（２）構成単位４
構成単位４は、上記式（４）で示される構成を有せば特に限定されない。式（４）中、Ｒ^４１が、水素、炭素数１〜３０のアルキル、炭素数６〜３０のアリールまたは炭素数７〜４０のアリールアルキルであり、これらのアルキル、アリールまたはアリールアルキルにおいて、少なくとも１つの水素がフッ素で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−が−Ｏ−またはシクロアルキレンで置き換えられてもよく；
Ｒ^４２が、架橋性、または非架橋性の基より選択される基である。
好ましくは、Ｒ^４１が、水素、炭素数１〜１０のアルキル、炭素数６〜１０のアリールまたは炭素数７〜２０のアリールアルキルであり、これらのアルキル、アリールまたはアリールアルキルにおいて、少なくとも１つの水素がフッ素で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−が−Ｏ−で置き換えられてもよい。
好ましくは、Ｒ^４２が、ヒドロキシル、環状エーテルを含む一価の官能基、ハロゲン化アルキル、ブロックドイソシアネート、イソシアネート、アミノ及びカルボキシルから選択される基を有する基、水素、炭素数１〜１０のアルキルであり、少なくとも１つの水素がフッ素で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−が−Ｏ−で置き換えられてもよい。 -Arbitrary structural unit which may constitute the polymer of the present invention (structural unit 3, structural unit 4)
The polymer of the present invention is not particularly limited as long as it includes the structural unit 1 or the structural unit 1 and the structural unit 2, but the obtained polymer has water and oil repellency, antifouling properties, charge control characteristics, and resistance to solvents. In order to control various properties such as solubility, hardness, and feel, compatibility with the resin, and leveling properties, the structural unit 3 represented by the following formula (3) and the following formula (4) are used. The structural unit 4 may be included.

(1) Structural unit 3
The structural unit 3 is not particularly limited as long as it has the structure represented by the above formula (3). In formula (3), R ³¹ is hydrogen, alkyl having 1 to 30 carbons, aryl having 6 to 30 carbons or arylalkyl having 7 to 40 carbons, and in these alkyls, aryls or arylalkyls, at least 1 one of hydrogen may be replaced by fluorine, and at least one -CH 2 _- may be replaced by -O- or cycloalkylene;
R ³² is a group selected from a crosslinkable or non-crosslinkable group.
Preferably, R ³¹ is hydrogen, alkyl having 1 to 10 carbons, aryl having 6 to 10 carbons or arylalkyl having 7 to 20 carbons, and in these alkyls, aryls or arylalkyls, at least one hydrogen is it may be replaced by fluorine, and at least one -CH 2 _- may be replaced by -O-.
Preferably, R ³² is a group having a group selected from hydroxyl, monovalent functional group including cyclic ether, alkyl halide, blocked isocyanate, isocyanate, amino and carboxyl, hydrogen, alkyl having 1 to 12 carbons, Aryl having 6 to 10 carbon atoms or arylalkyl having 7 to 20 carbon atoms, in which at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — May be replaced by -O-.
(2) Structural unit 4
The structural unit 4 is not particularly limited as long as it has the structure represented by the above formula (4). In formula (4), R ⁴¹ is hydrogen, alkyl having 1 to 30 carbons, aryl having 6 to 30 carbons or arylalkyl having 7 to 40 carbons, and in these alkyls, aryls or arylalkyls, at least One hydrogen may be replaced by fluorine, and at least one —CH ₂ — may be replaced by —O— or cycloalkylene;
R ⁴² is a group selected from crosslinkable or non-crosslinkable group.
Preferably, R ⁴¹ is hydrogen, alkyl having 1 to 10 carbons, aryl having 6 to 10 carbons or arylalkyl having 7 to 20 carbons, and in these alkyls, aryls or arylalkyls, at least one hydrogen There may be replaced by fluorine, and at least one -CH 2 _- may be replaced by -O-.
Preferably, R ⁴² is a group having a group selected from hydroxyl, a monovalent functional group including cyclic ether, halogenated alkyl, blocked isocyanate, isocyanate, amino and carboxyl, hydrogen, alkyl having 1 to 10 carbons. Wherein at least one hydrogen may be replaced with fluorine and at least one —CH ₂ — may be replaced with —O—.

[Organic solvent]
An organic solvent may be added to the curable resin composition of the present invention to form a coating liquid. Examples of organic solvents used include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, Chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, Benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-di) Cylformamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbon Solvents (perfluoropentane, perfluorohexane), cycloaliphatic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), aromatic Fluorine solvents (α, α, α-trifluorotoluene, hexafluorobenzene) and water are included. These may be used alone or in combination of two or more.
The amount of the organic solvent used is not particularly limited, but the organic solvent is preferably 0.1 to 2 times, more preferably 1 to 1.5 times the total solid content of the curable resin composition. It is.

[Additive]
The curable resin composition of the present invention may contain an antioxidant. By containing an antioxidant, oxidation deterioration can be prevented and a film with less coloring can be obtained. Examples of antioxidants are phenolic, sulfur and phosphorus antioxidants. Although the content rate of the preferable antioxidant when using the antioxidant is not particularly limited, the antioxidant is preferably 0.0001 to 0.1 weight based on the total solid content of the curable resin composition. %, More preferably 0.01 to 0.1% by weight.

  Specific examples of the antioxidant include monophenols (2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), bisphenols (2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxy Saspiro [5,5] undecane, etc.), polymer type phenols (1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2) , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) Propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-) t-butyl-4′-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc.), sulfur-based antioxidant (dilauryl-3,3′-thiodipropio) , Dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate), phosphites (riphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (Nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2 , 4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl- 4- {2- (octadecyloxy Rubonyl) ethyl} phenyl] hydrogen phosphite), and oxaphosphaphenanthrene oxides (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-) t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide etc.). These antioxidants can be used alone, but it is particularly preferable to use them in combination with phenolic / sulfuric or phenolic / phosphorous. As commercially available phenolic antioxidants, IRGANOX 1010 (trade name) and IRGAFOS 168 (trade name) manufactured by Ciba Japan Co., Ltd. can be used singly or in combination. You can also.

  In order to improve light resistance, the curable resin composition may contain an ultraviolet absorber. As the ultraviolet absorber, a general ultraviolet absorber for plastics can be used, and the preferred content is not particularly limited. The ultraviolet absorber is preferably 0.0001 to 0.1% by weight, more preferably 0.001 to 0.1% by weight, based on the total solid content of the curable resin composition.

  Specific examples of the ultraviolet absorber include salicylic acids such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy- Benzophenones such as 5-sulfobenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3 ' 5′-ditert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′) , 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-3) Benzotriazoles such as', 3 '', 4 '', 5 '', 6 ''-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, and bis (2,2,6,6-tetramethyl -4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Ntamechiru 4-piperidyl) is [{3,5-bis (1,1-dimethylethyl) -4-hydrido hydroxyphenyl} methyl] hindered amines such as butyl malonate.

[Other additives]
Or, to improve the durability of photochromic dyes, improve the color development rate, improve the fading rate and improve the moldability, surfactants, radical scavengers, UV stabilizers, mold release agents, anti-coloring agents, electrification Arbitrary components such as an inhibitor, a fluorescent dye, a dye, a pigment, a fragrance, and a plasticizer may be contained in the curable resin composition.
Alternatively, an optional component such as an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiation aid, a leveling agent, a wettability improver, a silane coupling agent, and a curing aid may be contained in the curable resin composition. Good.
As these additives, known compounds can be used without any limitation.

  As a hardening adjuvant which improves the adhesiveness of the hard-coat layer of this invention, and a base material, the compound which has 2 or more of thiols in 1 molecule is mentioned, for example. More specifically, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, Methylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglyconate, trishydroxyethyltristhiopropionate, 1,4-bis (3-mercaptobuti Ryloxy) butane (trade name; Karenz MT BD1, manufactured by Showa Denko KK), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name; Karenz) TPE1, manufactured by Showa Denko KK, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (product) Name: Karenz MT NR1, manufactured by Showa Denko KK).

[Preparation of curable resin composition]
In this invention, the preparation method of curable resin composition is not specifically limited, It can carry out by weighing and mixing a predetermined amount of each component. The order of adding each component is not particularly limited, and all the components may be added simultaneously, or only the monomer components may be mixed in advance, and the chromic compound or other components may be added and mixed immediately before polymerization. .

[Laminate]
Laminates 10 and 20 according to the second embodiment of the present invention are prepared by applying the curable resin composition of the present invention or the coating liquid containing the curable resin composition on one side of the substrate 2 (see FIG. 1). Alternatively, the energy (heat, active energy) required to form a layer by coating on both sides (see FIG. 2) and to cure the curable resin composition or the coating liquid layer containing the curable resin composition. Can be produced by irradiation and curing. The layer obtained by curing the curable resin composition or the coating liquid containing the curable resin composition becomes the hard coat layer 1 having a chromic function, and can improve the scratch resistance and wear resistance of the substrate 2. .

  The laminated bodies 10 and 20 can be manufactured from the curable resin composition by the following method. The laminates 10 and 20 of the present invention are obtained by a step of forming a curable resin composition of the present invention or a coating liquid layer containing the curable resin composition and a step of curing the layer.

Formation of a layer can be performed by apply | coating the coating liquid containing a curable resin composition or a curable resin composition to the single side | surface or both surfaces of a base material, for example.
The coating method is not particularly limited, but spin coating method, roll coating method, slit coating method, dipping method, spray coating method, gravure coating method, reverse coating method, rod coating method, bar coating method, die coating method, kiss coating method. A reverse kiss coating method, an air knife coating method, a curtain coating method, etc. can be used.
Examples of substrates to be applied include glass substrates such as white plate glass, blue plate glass, silica coated blue plate glass; polycarbonate, allyl diglycol carbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide Synthetic resin films such as triacetate and diacetate; cycloolefin resins including norbornene resins (trade names; Zeonoa, Zeonex, Nippon Zeon Co., Ltd., trade names; Arton, JSR Corporation), methacrylstyrene, polysulfone, alicyclic Transparent resin substrate used for optical applications such as acrylic resin and polyarylate; metal substrate such as aluminum plate, copper plate, nickel plate and stainless steel plate; other ceramic substrate, semiconductor substrate having photoelectric conversion element; urethane rubber, steel Ngomu and the like. These base materials may be pretreated. Examples of the pretreatment include chemical treatment with a silane coupling agent, sandblast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, gas treatment. Examples include a phase reaction method and vacuum deposition.

The curing of the layer can be performed as necessary, for example, when a solvent is used, and then usually performed by at least one of a heating step and an active energy ray irradiation step.
The applied curable resin composition or the coating liquid containing the curable resin composition may be dried at a temperature at which the solvent used is vaporized, and is usually performed at room temperature (about 25 ° C.) to about 120 ° C. Can do. In the heating step, the thermosetting resin can be cured in an environment of about 200 ° C. from the temperature at which thermosetting starts. When an active energy ray polymerization initiator is used as the curing agent, it can be cured by irradiation with a photoactive energy ray or an electron beam from an active energy ray source after drying. There are no particular restrictions on the active energy ray source, but depending on the nature of the active energy ray polymerization initiator used, for example, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, gas laser, solid state laser And an electron beam irradiation apparatus.

  Although the thickness of the hard-coat layer 1 is not specifically limited, Generally the film thickness should just be 0.1-50 micrometers, Preferably it is 0.1-25 micrometers, More preferably, it is 0.1-10 micrometers. Moreover, when the base material 2 is a film, the thickness is not particularly limited, but generally may be a film thickness of 0.1 μm to 1 mm, preferably 0.1 to 500 μm, more preferably 20 to 300 μm. is there. Although it will not specifically limit if the base material 2 is a lens, 1-10 mm is preferable.

  When the laminates 10 and 20 are used as optical films, the substrate 2 is not particularly limited as long as it is a material used for optical films. For example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, polyurethane, diacetyl cellulose , Triacetylcellulose, polyimide, and polyethersulfone. Among these, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, diacetyl cellulose, and triacetyl cellulose are preferable. These films may be purchased from commercial products. For example, “Lumirror 100-U34 (trade name)” manufactured by Toray Industries, Inc. can be used as a polyethylene terephthalate film having a thickness of 100 μm.

[Usage]
Since the hard coat layer of the present invention contains a chromic compound, it exhibits chromism. For example, when a photochromic compound is used, the laminate of the present invention consisting of a transparent base material and a hard coat layer is used for a sunglasses utilizing photoresponsiveness that develops color when light is irradiated and fades when light irradiation is stopped. It can be used as a lens. Even when the lens is composed of two layers of a base material and a hard coat layer, the lens exhibits chromism and can be a lens excellent in scratch resistance and wear resistance. Thus, the product which has a chromic function can be manufactured with a less layer structure because a hard-coat layer expresses chromism. Examples of products other than sunglasses lenses include helmet shields, windows such as car sunroofs, and window (window) films.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the contents described in the following examples.

[Example 1]
Preparation of UV curable coating agent A Urethane acrylate resin UV-1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100 wt%) 6.4 g as curable resin, organosilica sol PGM-AC-2140Y (as inorganic fine particles) Nissan Chemical Industries, Ltd., average particle size 30 nm, solid content concentration 40 wt%) 4.0 g, Irgacure 127 (BASF Japan, solid content concentration 100 wt%) 0.32 g as a polymerization initiator, silicon-containing compound XUA008 (manufactured by JNC Corporation, solid concentration 30 wt%) 0.267 g, propylene glycol monomethyl ether (PGNE, manufactured by Wako Pure Chemical Industries, Ltd.) 8.0 g, methyl ethyl ketone (MEK, manufactured by Wako Pure Chemical Industries, Ltd.) ) 2.0 g, DAE0018 (manufactured by Yamada Chemical Co., Ltd.) as a chromic compound A coating agent A (Example 1) was prepared by weighing 0.2 g of a solid content concentration of 100 wt% and stirring and mixing with a parallel stirrer (SRS261PA, ADVANTEC).
[Examples 2-7, Comparative Examples 1-5]
UV curable coating agents B to L were prepared as described below and used as Examples 2 to 7 and Comparative Examples 1 to 5.
Preparation of coating agent B and coating agent C Instead of the inorganic fine particles PGM-AC-2140Y of Example 1, organosilica sol MEK-ST-2040 (manufactured by Nissan Chemical Industries, Ltd., average particle size of 10 to 15 nm, solid content) A coating agent B (Example 2) was obtained by weighing 4.0 g (concentration 40 wt%) and stirring and mixing with a magnetic stirrer.
Further, a coating agent C (Example 3) having a different blending ratio of MEK-ST-2040 was used.
-Preparation of coding agent D and coating agent E Instead of the inorganic fine particles PGM-AC-2140Y of Example 1, organozirconia sol OZ-S30K-AC (manufactured by Nissan Chemical Industries, Ltd., average particle size 10-15 nm, solid) A coating agent D (Example 4) was obtained by weighing 5.3 g of a partial concentration of 30 wt% and stirring and mixing with a magnetic stirrer.
Moreover, the thing from which the compounding ratio of OZ-S30K-AC differs was set as the coating agent E (Example 5).
・ Preparation of coating agent F and coating agent G Instead of UV-1700B, 6.4 g of Aronix M305 (manufactured by Toagosei Co., Ltd., solid content concentration 100 wt%) was weighed and stirred and mixed with a magnetic stirrer. It was set as the coating agent F (Example 6).
Further, a coating agent G (Example 7) having a different mixing ratio of Aronix M305 was used.
-Preparation of Coating Agent H Coating Agent H (Comparative Example 1) was a coating agent A that did not contain inorganic fine particles and silicon-containing compounds.
-Preparation of Coating Agent I A coating agent I (Comparative Example 2) was a coating agent A that did not contain inorganic fine particles.
-Preparation of coating agent J and coating agent K The coating agent J (comparative example 3) with respect to the coating agent A did not contain a silicon-containing compound.
Further, a coating agent K (Comparative Example 4) having a different blending ratio was used.
-Preparation of coating agent L For coating agent A, inorganic fine particles are not contained, and instead of UV-1700B, 8.0 g of Aronix M305 (manufactured by Toagosei Co., Ltd., solid content concentration 100 wt%) is weighed, What was stirred and mixed with the magnetic stirrer was used as the coating agent L (comparative example 5).

Tables 1 and 2 show the weighed values when the coating agents A to L were prepared.

[Example 8]
-Preparation of thermosetting coating agent M Silaplane 4401 (manufactured by JNC Corporation, solid concentration 100 wt%) 1.225 g as the main polyol, and Takenate (manufactured by Mitsui Chemicals, Inc., solid) as the polyisocyanate of the curing agent (Partial concentration 74.8 wt%) 3.933 g, inorganic fine particles PGM-AC-2140Y (manufactured by Nissan Chemical Industries, Ltd., average particle size 30 nm, solid content concentration 40 wt%) 3.083 g, silicon-containing compound XUA008 (JNC ( Co., Ltd., solid concentration 30 wt%) 0.050 g, ethyl acetate (Kanto Chemical Co., Ltd.) 2.76 g, and DAE0018 (Yamada Chemical Co., Ltd., solid content concentration 100 wt%) as a chromic compound is 0.00. 125 g was weighed and stirred and mixed with a parallel stirrer (SRS261PA, ADVANTEC). Coating agent M (Example 8).

[Comparative Example 6]
A thermosetting coating agent O was prepared as described below and used as Comparative Example 6.
-Preparation of Coating Agent O Coating Agent O (Comparative Example 6) was a coating agent M containing no inorganic fine particles.

Table 3 shows the measured values when the coating agents M and O were prepared.

[Preparation of UV cured films A1 to L1 on a glass plate and evaluation of shielding ratio]
Using the coating agent A of Example 1, 300 rpm, 20 on a glass plate (manufactured by Eagle XG Corning Co., Ltd., 0.7 mm thickness) with a spin coater (Optical Coat MS-A150, manufactured by Mikasa Co., Ltd.) Spin coating was performed under the conditions of seconds to form a wet film. It is heat-treated for 1 minute on a hot plate (HI-200A, manufactured by AS ONE Co., Ltd.) set at 100 ° C. After that, a filter (U340, manufactured by HOYA) that cuts other than the wavelength of 290 to 370 nm was put on the sample, and a conveyor type ultraviolet irradiation device (MJ-1500L, manufactured by Eye Graphics) provided with a metal halide lamp. Was used for photocuring under conditions of 1000 mJ / cm ² to prepare a UV cured film A1 having a thickness of about 10 μm.
As soon as the UV cured film A1 was formed, the thickness of the coating film was measured using a surface roughness / fine shape measuring device (P-16 +, manufactured by KLA-Tencor).
Then, the transmittance | permeability in 575 nm was measured with the ultraviolet visible light photometer (V-670, JASCO Corporation make), the light absorbency in the case of a film thickness of 10 micrometers was calculated according to the following calculation methods, and this was shielded Rate.
Shielding rate = absorbance (Abs.) = Log 10 (transmittance / 100) × 10 / film thickness (μm)
The shielding rate was measured with a cured film + glass plate. The measurement results were as shown in Table 4.

Using the coating agents B to L of Examples 2 to 7 and Comparative Examples 1 to 5, a cured film on a glass plate was prepared in the same manner as the UV cured film A1, and UV cured films B1, C1,. It was.
The measurement results of the shielding rates of the obtained UV cured films B1, C1,... Were as shown in Tables 4 and 5.

Tables 4 and 5 show measured values of the cured films A1 to L1.

[Production and Evaluation of UV Curing Type Coated Sheets A2 to L2 on Polycarbonate Sheet]
-Preparation of UV cured film on polycarbonate sheet Using coating agent A of Example 1, coating rod No. 1 on a polycarbonate sheet (Iupilon NF2000, Mitsubishi Engineering Plastics Co., Ltd., 0.5 mm thickness). 16 (manufactured by RDS Webster Co., Ltd.), a wet film was formed, and heat treatment was performed for 3 minutes in an oven (LP-201, manufactured by ESPEC Co., Ltd.) set at 80 ° C. After that, using a conveyor type ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) equipped with a high pressure mercury lamp, it is photocured under conditions of an integrated light quantity of 500 mJ / cm ² to obtain a UV curable coated sheet A2 having a film thickness of about 5 μm. It was.
Table 6 shows the measurement results of the total light transmittance, abrasion resistance test, adhesion, pencil hardness test, and liquid repellency test of the obtained UV curable coated sheet A2.

Using the coating agents B to L of Examples 2 to 7 and Comparative Examples 1 to 5, coating was performed in the same manner as the UV curable coat sheet A2, and UV curable coat sheets B2 to L2 were obtained.
Table 6 shows the measurement results of the total light transmittance, abrasion resistance test, adhesion, pencil hardness test, and liquid repellency test of the obtained UV curable coat sheets B2 to L2.

[Measurement method of total light transmittance, abrasion resistance test, adhesion, pencil hardness test, liquid repellency test]
The physical property values of the coating films of the UV curable coat sheet A2 and the UV curable coat sheets B2 to L2 were measured by the following methods.

  The total light transmittance (% T) was measured based on JIS K7361 using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

In the abrasion resistance test, steel wool (Bonster product number # 0000, manufactured by Nippon Steel Wool) was used, and a 1 kg load, 1000 reciprocal scratch test was performed with a scratch tester. The change (Δhaze) of the haze value (%) of the film before and after the scratch test was measured with a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in the same manner as the measurement of the total light transmittance (% T). did.
Δ haze = haze after test (%)-haze before test (%, initial haze)

For the adhesion, a cross-cut test was performed in which cellophane tape (manufactured by Teraoka Manufacturing Co., Ltd.) was rubbed against a cross wound made with a cutter against the coating film and then peeled off. The evaluation criteria are as follows. All were confirmed visually.
○: No change.
(Triangle | delta): A part of coating film around a cross wound has peeled off.
X: The coating film on the surface to which the cellophane tape is adhered is peeled off.

  The pencil hardness test was measured according to JIS K5600 using a surface property tester (HEIDON Type: 14W, manufactured by Shinto Kagaku Co., Ltd.).

For the liquid and oil repellency test, a 3 mm x 30 mm line was drawn on the coating film using an oil-based sign pen (Sharpie Marker, black, King Size Pro Permanent Markers, Sharpie, hereinafter referred to as “marker”). It was confirmed. Moreover, the coating film after drawing a line with the marker was wiped 3 times with Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd.), and the line with the marker on the coating film was evaluated by visual confirmation according to the following evaluation criteria. .
○: The line written with the marker disappeared completely.
Δ: Some lines written with markers remained.
X: The line written with the marker did not disappear.

Tables 6 and 7 show the measured values of the UV curable coat sheets A2 to L2.

[Preparation of thermosetting films M1 and O1 on glass plate and evaluation of shielding ratio]
Using the coating agent M of Example 8, 1500 rpm, 30 on a glass plate (manufactured by Eagle XG Corning Co., Ltd., 0.7 mm thickness) with a spin coater (Optical Coat MS-A150, manufactured by Mikasa Co., Ltd.) Spin coating was performed under the conditions of seconds to form a wet film. It is heat-treated for 1 minute on a hot plate (HI-200A, manufactured by AS ONE Co., Ltd.) set at 100 ° C. Thereafter, heat treatment was performed for 90 minutes in a clean oven (Ymato Clean Even DT610, manufactured by Yamato Kagaku Co., Ltd.) set at 130 ° C. to produce a thermosetting film M1 having a thickness of about 10 μm.
As soon as the thermosetting film M1 was formed, the thickness of the coating film was measured using a surface roughness / fine shape measuring device (P-16 +, manufactured by KLA-Tencor).
Then, the transmittance | permeability in 575 nm was measured with the ultraviolet visible light photometer (V-670, JASCO Corporation make), the light absorbency in the case of a film thickness of 10 micrometers was calculated according to the following calculation methods, and this was shielded Rate.
Shielding rate = absorbance (Abs.) = Log 10 (transmittance / 100) × 10 / film thickness (μm)
The shielding rate was measured with a cured film + glass plate. The measurement results were as shown in Table 8.

Using the coating agent O of Comparative Example 6, a cured film on a glass plate was produced in the same manner as the thermosetting film M1, and a thermosetting film O1 was obtained.
The measurement result of the shielding rate of the obtained thermosetting film O1 was as shown in Table 8.

Table 8 shows the measured values of the cured films M1 and O1.

[Production and Evaluation of Thermosetting Coated Sheets M2 and O2 on Polycarbonate Sheet]
-Production of thermosetting film on polycarbonate sheet Using coating agent M of Example 8, coating rod No. 1 on a polycarbonate sheet (Iupilon NF2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd., 0.5 mm thickness). 22 (made by R.D.S. Webster Co., Ltd.), a wet film was formed, heat-treated for 90 minutes in an oven (LP-201, manufactured by ESPEC Co., Ltd.) set at 130 ° C., and thermally cured. A thermosetting coated sheet M2 having a thickness of about 5 μm was obtained.
Table 9 shows the measurement results of the total light transmittance, abrasion resistance test, adhesion, pencil hardness test, and liquid repellency test of the obtained thermosetting coat sheet M2.

Using the coating agent O of Comparative Example 6, coating was performed in the same manner as for the thermosetting coat sheet M2, to obtain a thermosetting coat sheet O2.
Table 9 shows the measurement results of the total light transmittance, abrasion resistance test, adhesion, pencil hardness test, and liquid repellency test of the obtained thermosetting coated sheet O2.

[Measurement method of total light transmittance, abrasion resistance test, adhesion, pencil hardness test, liquid repellency test]
The physical property values of the coatings of the thermosetting coat sheet M2 and the thermosetting coat sheet O2 were measured by the following methods.

  The total light transmittance (% T) was measured based on JIS K7361 using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

For the abrasion resistance test, steel wool (Bonster product number # 0000, manufactured by Nippon Steel Wool) was used, and a 400 g load, 30 reciprocal scratch test was performed with a scratch tester. The haze change (Δhaze) of the film before and after the scratch test was measured with a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).
Δ haze = haze after test (%)-haze before test (%, initial haze)

For the adhesion, a cross-cut test was performed in which cellophane tape (manufactured by Teraoka Manufacturing Co., Ltd.) was rubbed against a cross wound made with a cutter against the coating film and then peeled off. The evaluation criteria are as follows. All were confirmed visually.
○: No change.
(Triangle | delta): A part of coating film around a cross wound has peeled off.
X: The coating film on the surface to which the cellophane tape is adhered is peeled off.

  The pencil hardness test was measured according to JIS K5600 using a surface property tester (HEIDON Type: 14W, manufactured by Shinto Kagaku Co., Ltd.).

For the liquid and oil repellency test, a 3 mm x 30 mm line was drawn on the coating film using an oil-based sign pen (Sharpie Marker, black, King Size Pro Permanent Markers, Sharpie, hereinafter referred to as “marker”). It was confirmed. Moreover, the coating film after drawing a line with the marker was wiped 3 times with Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd.), and the line with the marker on the coating film was evaluated by visual confirmation according to the following evaluation criteria. .
○: The line written with the marker disappeared completely.
Δ: Some lines written with markers remained.
X: The line written with the marker did not disappear.

Table 9 shows measured values of the thermosetting coat sheets M2 and O2.

As is clear from the results of Tables 4, 5 and 8, the cured films of Examples 11 to 18 are excellent in shielding rate. Further, as is clear from the results in Table 6, Examples 21 to 27 also have wear resistance and water / oil repellency. The shielding rate, abrasion resistance, and water / oil repellency are particularly excellent because they are formed from a silicon-containing compound and inorganic fine particles.
As described above, the cured film formed from the coating agent (curable resin composition) of the present invention has excellent shielding properties when irradiated with ultraviolet rays, and further wear resistance when UV curable acrylate resin is used. The effect of water and oil repellency is seen.

The graph of FIG. 3 shows the relationship between the shielding rates of Examples 11 to 15 and the content of inorganic fine particles. The resin is urethane acrylate, and the addition amount of the chromic compound is the same. As is apparent from the graph, when the inorganic fine particles 1, 2, and 3 were added, when the silicon-containing compound was used in combination, the effect of increasing the shielding rate was observed as the proportion of the inorganic fine particles increased.
The graph of FIG. 4 shows the relationship between the shielding rates of Examples 16 to 17 and the content of inorganic fine particles. The resin is an acrylate, and the addition amount of the chromic compound is the same. As is apparent from the graph, when the silicon-containing compound was used in combination, the shielding rate increased as the proportion of the inorganic fine particles increased.
The graph of FIG. 5 shows the relationship between the shielding rates of Comparative Examples 11, 13, and 14 and the content of inorganic fine particles. The resin is urethane acrylate, and the addition amount of the chromic compound is the same.
As compared with Examples 11 to 15, in Comparative Examples 11, 13, and 14 in which no silicon-containing compound was used in combination, the effect of increasing the shielding rate was not observed as the proportion of inorganic fine particles increased.
The graph of FIG. 6 shows the relationship between the shielding rate of Example 18 and the content of inorganic fine particles. The resin is a thermosetting resin, and the addition amount of the chromic compound is the same. Also in the thermosetting resin, when the proportion of inorganic fine particles increased in the state where the silicon-containing compound was used in combination, the effect of increasing the shielding rate was observed.

DESCRIPTION OF SYMBOLS 1 Hard coat layer which has chromic function 2 Base material 10 and 20 Laminate

Claims (15)

Inorganic fine particles having an average particle size of 0.01 to 10 μm;
A chromic compound;
At least one curable resin selected from the group consisting of a thermosetting resin and an active energy ray curable resin;
Containing a silicon-containing polymer;
Curable resin composition. Containing 10 wt% to 70 wt% of the inorganic fine particles with respect to the total solid content of the curable resin composition,
The curable resin composition according to claim 1. The inorganic fine particles are at least one particle selected from the group consisting of silicon dioxide, zirconium dioxide, tin oxide, and alumina, and an average particle diameter is 0.01 to 0.05 μm.
The curable resin composition of Claim 1 or Claim 2. The chromic compound is a photochromic compound,
The curable resin composition of any one of Claims 1-3. The photochromic compound is at least one compound selected from the group consisting of spiropyran compounds, spirooxazine compounds, naphthopyran compounds, fulgimide compounds, chromene compounds, and diarylethenes.
The curable resin composition according to claim 4. The curable resin is an active energy ray curable resin.
Curable resin composition of any one of Claims 1-5. The active energy ray-curable resin is at least selected from the group consisting of (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins. One compound,
The curable resin composition according to claim 6. The active energy ray-curable resin is a urethane (meth) acrylate resin having a bifunctional or higher functional (meth) acryloyl group.
The curable resin composition according to claim 7. The silicon-containing polymer contains a fluorine silsesquioxane compound,
The curable resin composition of any one of Claims 1-8. The silicon-containing polymer includes a structural unit 1 represented by the following formula (1), and further includes a structural unit 2 represented by the following formula (2).
The curable resin composition of any one of Claims 1-9.

(In the above formula (1), R _f ^{1 to} R _f ⁷ are each independently fluoroalkyl having 1 to 20 carbon atoms in which at least one methylene may be replaced by oxygen, and at least one hydrogen is fluorine or C6-C20 fluoroaryl substituted with trifluoromethyl or C7-C20 fluoroarylalkyl in which at least one hydrogen in aryl is replaced with fluorine or trifluoromethyl;
L ¹ is —Y ¹ —O—CO— (wherein Y ¹ is an alkylene having 2 to 10 carbon atoms bonded to Si), and R ¹⁰ is hydrogen or 1 to 5 carbon atoms. Alkyl or aryl having 6 to 10 carbon atoms;
Or L ¹ is —Y ² —Ph— (wherein Y ² is a single bond or alkylene having 1 to 10 carbon atoms bonded to Si, and Ph is phenylene), and R ¹⁰ Is hydrogen. )

(In the above formula (2), n is an integer of 1 to 1,000;
R ^{1 to} R ⁷ are each independently hydrogen, alkyl, aryl or arylalkyl, in which at least one hydrogen may be replaced by fluorine, and at least one methylene May be replaced by oxygen or cycloalkylene;
L ² is —Y ¹ —O—CO— (wherein Y ¹ is an alkylene having 2 to 10 carbon atoms bonded to Si), and R ²⁰ is hydrogen, linear or branched. Or an alkyl having 1 to 5 carbon atoms or an aryl having 6 to 10 carbon atoms;
L ² is —X ¹ —Y _p —O—CO— (wherein X ¹ is an alkylene having 2 to 20 carbon atoms bonded to Si, and Y _p is —OCH ₂ CH ₂ —, —OCHCH _3. CH ₂ — or —OCH ₂ CH (CH ₃ ) —, p is an integer of 0 to 3), and R ²⁰ is hydrogen, alkyl having 1 to 5 carbons, or 6 to 10 carbons. Or L ² is -Y ² -Ph- (wherein Y ² is a single bond or alkylene having 1 to 10 carbon atoms bonded to Si, and Ph is phenylene). And R ²⁰ is hydrogen. ) Further containing an organic solvent,
The organic solvent is at least one solvent selected from the group consisting of aromatic and aliphatic hydrocarbons, ethers, esters, alcohols, and ketones.
The curable resin composition of any one of Claims 1-10. A substrate;
A hard coat layer obtained by curing the curable resin composition according to claim 1,
Laminated body. The base material is glass, plastic, metal, or ceramics.
The laminate according to claim 12. The plastic is polyethylene terephthalate (PET), polycarbonate, nylon, or allyl diglycol carbonate.
The laminate according to claim 12 or claim 13. A lens comprising the laminate according to any one of claims 11 to 14;
A frame for holding the lens;
Glasses.

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