JP2006160802A - Stain resistance-imparting agent, cured product and article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stain resistance-imparting agent having excellent hardness and scratch resistance, a cured product and an article by using the imparting agent. <P>SOLUTION: The stain resistance-imparting agent contains an organic inorganic complex comprising fine inorganic oxide particles (B) and an organic polymer (A) bonding to the fine inorganic oxide particles through O-Si-R- (R expresses a 2-10C straight chain or branched alkylene group) bonds. The organic polymer (A) has a stain resistance-imparting group and a group independent of the stain resistance-imparting group and polymerizable by irradiating with active energy rays. A 5μm thick film formed by applying the organic inorganic complex on a PET base having 100 μm thickness and irradiating with active energy rays to polymerize the complex has ≥F pencil hardness and ≥80° contact angle to water. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a stain resistance imparting agent having excellent hardness and scratch resistance, and a cured product and an article using the imparting agent. In particular, the present invention relates to a stain resistance imparting agent that provides a coating film having sufficient performance even in a thin film.

  Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene copolymer (ABS), methyl methacrylate styrene copolymer (MS resin), acrylonitrile styrene copolymer (AS resin), etc. Resin materials such as styrene-based resin, vinyl chloride-based resin, and cellulose acetate such as triacetyl cellulose are particularly excellent in lightness, ease of processing, and impact resistance. It is used for various applications such as plates, window materials, roofing materials, packaging materials, various housing materials, optical disk substrates, plastic lenses, liquid crystal displays, plasma displays, and substrates of display devices such as projection TVs.

However, since these plastic products have low surface hardness, they are easily damaged, and transparent resins such as polycarbonate and polyethylene terephthalate have a drawback that the original transparency or appearance of the resin is significantly impaired. This makes it difficult to use plastic products in fields that require wear resistance.
Under such circumstances, there is a need for an active energy ray-curable hard coat material (coating material) that imparts wear resistance to the surface of a plastic product. However, since the cured layer of the commercially available active energy ray-curable hard coat material has a large shrinkage, warpage, peeling or cracking, it is difficult to apply a thick layer, which can be achieved as a result. There were limits to hardness and scratch resistance.

  In order to solve such problems, various active energy ray-curable coating agents have recently been proposed that realize hardness and wear resistance that surpass conventional methods. For example, as described in Patent Document 1, two or more coating agents are coated, and the outermost layer is formed of an inorganic coating material such as polysilazane and having a film-forming property. Has been shown to improve significantly (Patent Document 1). However, since the coating agent is inorganic, it is difficult to increase the thickness of the coating agent, and it is substantially necessary to apply two or more layers.

On the other hand, attempts have been made to improve hardness and wear resistance by coating two or more coating agents having different elastic moduli. For example, Patent Document 2 describes that a coating film having high hardness can be obtained by making the elastic modulus of the second layer coating agent larger than that of the first layer coating agent (Patent Document 2). . Patent Document 3 describes that a coating film having high hardness can be obtained by setting the elastic modulus of the first layer coating agent to be larger than the elastic modulus of the second layer coating agent ( Patent Document 3). However, in both cases, the total thickness of the coating film becomes 10 μm or more, and two or more layers are applied, so that productivity is poor.
Furthermore, in Patent Document 4, a methacrylic polymer is applied to the first layer, and a coating layer obtained by curing an organosiloxane resin composed of a hydrolytic condensate of colloidal silica and a specific silicate is laminated on the second layer. In addition, it is described that the total thickness of the coat film is 10 μm or less and that excellent wear resistance can be realized. However, there is no change in the application of two or more layers (Patent Document 4).

  On the other hand, coating agents that can realize excellent hardness and wear resistance even with single-layer coating have been studied. Compositions of colloidal silica and polyfunctional acrylates, and hydrolyzing / condensation compositions of colloidal silica and specific silicates, and curable resin compositions of these with polyfunctional acrylates, epoxy resins or phenoxy resins, or the like A composition of this and a polymer such as an acrylic resin has been widely studied as an organic / inorganic composite coating agent. However, these have problems such as insufficient hardness and wear resistance level, poor stability of the coating liquid, and insufficient environmental resistance (humidity resistance, heat resistance, etc.) of the cured film. . Compared with these, the active energy ray-curable coating agent based on a compound obtained by reacting a polyfunctional acrylate and colloidal silica as described in Patent Documents 5 and 6 is a conventional organic / inorganic composite. Compared to the coating agent, even with single-layer coating, the hardness and wear resistance are excellent. However, the stain resistance and weather resistance are low, and sufficient surface hardening cannot be obtained at the time of coating a thin film, making it difficult to express the physical properties that should be originally expressed (Patent Documents 5 and 6).

  For example, as shown in Patent Document 7, a method using a polymerized UV curable resin has also been proposed in order to reduce shrinkage (Patent Document 7). However, although curing shrinkage is greatly reduced, there is a limit to application to applications that require lower shrinkage and applications that require higher hardness and scratch resistance. In addition, it is susceptible to curing inhibition by oxygen, and in particular, there is a problem with curing with a thin film (for example, a film thickness of 2 μm or less). There were many.

  Furthermore, in order to further reduce shrinkage or increase the degree of curing of the surface, a method using a cationically polymerizable resin as a (polymerized) UV curable resin (for example, Patent Document 8), cationic polymerization is possible. A method using colloidal silica bonded with a low molecular weight organic component (for example, Patent Document 9), a method using these components together with a normal radical polymerizable UV curable resin (including both organic and organic / inorganic hybrids) ( For example, Patent Literature 10, Patent Literature 11, Patent Literature 12, Patent Literature 13 and the like have been proposed. Although there is a feature in reducing shrinkage, increasing film thickness, or increasing the degree of hardening of the surface, there are still limitations in application to applications that require higher hardness and scratch resistance. Further, there are still many problems in imparting contamination resistance and weather resistance.

By the way, there are many examples of stain-resistant coating agents (for example, coating films obtained from specific fluorine-containing polymers or silicone-containing polymers (Patent Document 14, Patent Document 15, Patent Document 16, Patent Document 17, However, there has been a problem in the durability of the performance, particularly the antifouling durability when scratched.
As a method for solving such a problem, the present inventor has an active energy ray curing containing a copolymer containing an acrylic group and a polysiloxane group in the side chain, and optionally containing a fluorine-containing alkyl group as an essential component. Various compositions have been studied (for example, Patent Document 19, Patent Document 20, Patent Document 21, etc.). Further, for example, in Patent Document 22, an active energy ray-curable resin composition containing a copolymer having a fluorine or polysiloxane group and simultaneously containing an acrylic group has a balance of stain resistance, high hardness and scratch resistance. It is described that an excellent cured film is formed.
Although the stain resistance and durability of the coating films obtained from these compositions are relatively good, the level of demand for stain resistance has increased in recent years, and in particular, writing and erasing with the recently developed blue laser For use in next-generation optical discs, touch screen displays for car navigation systems, PDAs and mobile phones, large screen flat panel TV displays such as liquid crystal televisions and plasma TVs, etc., it has not been sufficient in performance. This is because such a stain-resistant copolymer itself has a relatively low hardness and is not high in curability.
In particular, in such applications, coating is often performed with a thin film, and in such a case, there are many problems with respect to durability of physical properties and stain resistance.

JP-A-11-309814 JP 2000-52472 A JP 2000-214791 A JP 2000-21845 A Japanese Patent Laid-Open No. 5-287215 Japanese Patent Laid-Open No. 9-100111 JP 10-316864 A JP 2001-40205 A JP 2002-53659 A JP-A-9-278935 Japanese Patent Laid-Open No. 2002-128887 JP 2002-322430 A JP 2003-147017 A Japanese Patent Laid-Open No. 10-279834 JP 2002-37827 A JP 2002-241146 A JP 2003-165828 A JP 2003-313385 A JP 2000-80169 A JP 2001-98188 A JP 2002-194084 A JP 2003-335984 A

The present invention is intended to solve the above-described problems, and it is possible to increase hardness and impart wear resistance even with a thin film, and to provide excellent contamination resistance and durability of the contamination resistance. Provided is a stain resistance imparting agent that can be imparted.
Furthermore, it is to provide a stain resistance imparting agent or the like that can impart weather resistance while maintaining these performances, and can impart more excellent thin film and surface curability as required.

  As a result of intensive studies by the inventor under the above problems, it has been found that the above problems can be solved by the following means.

(1) Inorganic oxide fine particles (B) containing colloidal silica as a main component, and —O—Si—R— bonds (where R is a linear or branched alkylene group having 2 to 10 carbon atoms). And an organic-inorganic composite having an organic polymer (A) bonded through the organic polymer (A), wherein the organic polymer (A) is independent of the antifouling group and the antifouling group. A thickness formed by applying an active energy ray and polymerizing the organic-inorganic composite on a PET substrate having a thickness of 100 μm and irradiating the active energy ray. The 5 μm film has a pencil hardness of F or higher and a contact angle with respect to water of 80 degrees or higher.
(1-1) In the inorganic oxide fine particles (B), an organic component (A ′) having a (meth) acryloyl group further has an —O—Si—R— bond (R is a carbon number of 2 to 10). (It represents a linear or branched alkylene group.) The antifouling agent according to (1), which is bonded via
(2) The contamination resistance according to (1), wherein the stain resistance imparting group is at least one group selected from the group consisting of an organo (poly) siloxane group, an organic fluorine compound group, and a linear alkyl group having 12 or more carbon atoms. Sex imparting agent.
(2-1) The stain resistance-imparting group is at least one member selected from the group consisting of a perfluoroalkyl group, a perfluoroalkylene group, a polysiloxane group, and a linear alkyl group having 12 or more carbon atoms. Antifouling imparting agent.
(3) The antifouling agent according to (1) or (2), wherein the group capable of being polymerized by irradiation with active energy rays is a group capable of photocationic polymerization.
(4) The antifouling agent according to (3), wherein the photocationically polymerizable group is an epoxy group and / or an oxetane group.
(5) The antifouling agent according to (1) or (2), wherein the group capable of being polymerized by irradiation with active energy rays is a group capable of photoradical polymerization.
(6) The antifouling agent according to (5), wherein the radically polymerizable group is a (meth) acryloyl group.
(7) The stain resistance imparting agent according to any one of (1) to (6), comprising a cationically polymerizable photoinitiator (C).
(8) The stain resistance imparting agent according to any one of (1) to (7), which contains a radical polymerizable photoinitiator (D).

(9) Further, a radical polymerizable organic (meth) acrylate compound and / or a radical polymerizable organic (meth) acrylamide compound (E), a polymer (F) having a radical polymerizable group, an organic epoxy compound (G), and The antifouling agent according to any one of (1) to (8), which contains at least one member selected from the group consisting of organic oxetane compounds (H).
(10) Furthermore, ultraviolet absorber (I), hindered amine light stabilizer (J), antistatic agent (K), slipperiness imparting agent (L), antifogging imparting agent (M) and peelability imparting agent (N The antifouling agent according to any one of (1) to (9), which contains at least one member selected from the group consisting of:

(11) Further, inorganic oxide fine particles (B) mainly composed of colloidal silica, and —O—Si—R— bonds (where R is a linear or branched group having 2 to 10 carbon atoms). An organic-inorganic composite having an organic component (A ′) having a (meth) acryloyl group bonded via an alkylene group). Contaminant imparting agent.
(11-1) Furthermore, inorganic oxide fine particles (B) containing colloidal silica as a main component, and —O—Si—R— bonds (where R is a straight chain having 2 to 10 carbon atoms) An organic-inorganic composite having an organic component (A ′) having a number average molecular weight of 1000 or more having a (meth) acryloyl group in the side chain bonded via a branched alkylene group), (1) The stain resistance imparting agent according to any one of to (10).
(11-2) Furthermore, inorganic oxide fine particles (B) containing colloidal silica as a main component, and —O—Si—R— bonds (where R is a straight chain having 2 to 10 carbon atoms) (1) to (10) including an organic-inorganic composite having an organic component (A ′) having a number average molecular weight of 1000 or less having a (meth) acryloyl group bonded via a branched alkylene group. ) The stain resistance imparting agent according to any one of the above.
(12) A cured product obtained by polymerizing the stain resistance imparting agent according to any one of (1) to (11) by irradiation with active energy rays.
(13) An article having on its surface a film formed by polymerizing the antifouling agent according to any one of (1) to (11) by irradiation with active energy rays.
(13-1) The article according to (13), wherein the thickness of the film is 2 μm or less.
(13-2) The article according to (13), wherein the thickness of the film is 5 μm or more.
(13-3) In the film, the content of the stain resistance-imparting group at a position 3 nm thick from the surface of the film is at least three times the average content of the contamination-resistance imparting group in the entire film. The article according to (13).
(14) When the antifouling agent is applied on a PET substrate having a thickness of 100 μm and polymerized by irradiation with active energy rays, a film having a thickness of 3 nm is formed from the surface of the film. The antifouling agent according to any one of (1) to (11), wherein the content of the antifouling group at the position is at least three times the average content of the antifouling group in the entire film. .
(15) When the stain resistance imparting agent is applied onto a 100 μm thick PET base material and polymerized by irradiation with active energy rays, the film is usually in an oxygen concentration atmosphere. After curing, the stain resistance imparting agent according to any one of (1) to (11) and (14), wherein the abrasion resistance is 25.0 or less and the warpage amount is 1 mm or less.
(16) When the antifouling property-imparting agent is applied onto a PET substrate having a thickness of 100 μm and polymerized by irradiation with active energy rays, the film has a haze value of 1.5 μm. % Of the stain resistance imparting agent according to any one of (1) to (11), (14) and (15).
(17) Inorganic oxide fine particles (B) mainly composed of colloidal silica, and —O—Si—R— bonds (where R is a linear or branched alkylene group having 2 to 10 carbon atoms). And an organic-inorganic composite having an organic polymer (A) bonded through the organic polymer (A), wherein the organic polymer (A) is independent of the antifouling group and the antifouling group. A composition having a group capable of being polymerized by irradiation with active energy rays.
(18) The organic polymer (A) includes a contamination-resistant group-containing radical polymerizable monomer (A-1) 1 to 40% by weight, a group capable of being polymerized by irradiation with active energy rays, and / or 1 to 60% by weight of a radically polymerizable monomer (A-2) that can be introduced into a side chain, and a radically polymerizable monomer (A-3) that can be polymerized with the monomer (A-1) and the monomer (A-2). The composition according to (17), wherein 0 to 80% by weight is polymerized.
(19) Furthermore, inorganic oxide fine particles (B) mainly composed of colloidal silica, and —O—Si—R— bonds (where R is a linear or branched group having 2 to 10 carbon atoms). The composition according to (17) or (18), comprising an organic-inorganic composite having an organic component (A ′) having a (meth) acryloyl group bonded via an alkylene group.
(19-1) Furthermore, inorganic oxide fine particles (B) containing colloidal silica as a main component, and —O—Si—R— bonds (where R is a straight chain having 2 to 10 carbon atoms) An organic-inorganic composite having an organic component (A ′) having a number average molecular weight of 1000 or more having a (meth) acryloyl group in the side chain bonded via a branched alkylene group), (17) Or the composition as described in (18).
(19-2) Furthermore, inorganic oxide fine particles (B) containing colloidal silica as a main component, and —O—Si—R— bond (where R is a straight chain having 2 to 10 carbon atoms or An organic-inorganic composite having an organic component (A ′) having a number average molecular weight of 1000 or less having a (meth) acryloyl group bonded via a branched alkylene group), (17) or (18 ).
(20) Inorganic oxide fine particles (B) mainly composed of colloidal silica, and —O—Si—R— bonds (where R is a linear or branched alkylene group having 2 to 10 carbon atoms). An organic-inorganic composite having a stain resistance imparting group and a group capable of being polymerized by irradiation with an active energy ray independently of the stain resistance imparting group.

Since the stain resistance imparting agent of the present invention is less susceptible to oxygen inhibition due to the difference in polymerization termination reaction, it has a lower shrinkage than the addition polymerization of unsaturated bonds, so that both thinning and thickening are possible. became.
And the stain resistance imparting agent of the present invention has excellent curability, scratch resistance, transparency, and stain resistance even if the film is thinly applied to the surface of the article and cured. I decided to have it. Furthermore, it has become possible to enhance the durability of those performances.
For this reason, it can be suitably used in a wide range of applications (touch panel, display, mobile phone casing, automobile transparent part protection, agricultural (house) transparent part protection, optical disk (DVD) surface protection, etc.).
On the other hand, when the stain resistance-imparting agent of the present invention is thickly applied to the surface of an article or the like and cured, it is possible to combine excellent hardness. As a result, it can be suitably used in a wider range of applications.
In addition, the stain resistance-imparting agent of the present invention is a specific polyolefin-based substrate, acrylic-based substrate, fluororesin-based group, which is hard to adhere to a normal hard coat agent (particularly a stain-resistance imparting hard coat agent). The material also has the advantage of having excellent adhesion.
In particular, by adopting a cationically polymerizable group as a stain resistance imparting agent, excellent curability can be obtained even in a thin film, and effects such as an increase in hardness, stain resistance, and improvement in durability can be obtained. . In addition, by adopting a radical radical polymerizable group as a stain resistance imparting agent, photocation polymerization is particularly effective when an initiator excellent in thin film curability or an initiator relatively less susceptible to oxygen inhibition is used. As in the case of adopting possible groups, excellent curability can be obtained even in a thin film, and effects such as an increase in hardness, stain resistance, and improvement in durability can be obtained.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
The polymerization referred to in the present invention includes so-called copolymerization unless otherwise specified. Accordingly, the polymer includes a copolymer.
The room temperature referred to in the present invention refers to the temperature of the place where the experiment or the like is performed, for example, a temperature of 15 to 30 ° C., more preferably 20 to 25 ° C. The normal oxygen concentration means 18 to 22%, more preferably 19 to 21%.

  In the stain resistance imparting agent of the present invention, the inorganic oxide fine particles (B) mainly composed of colloidal silica and the organic polymer (A) are —O—Si—R— bonds (preferably —O—Si—R). -S-bond) (R represents a linear or branched alkylene group having 2 to 10 carbon atoms) (A) (B) (hereinafter referred to as (A) (B ) May be referred to as a complex). Furthermore, the organic polymer (A) has a stain resistance imparting group and a group capable of being polymerized by irradiation with active energy rays independently of the stain resistance imparting group. Hereinafter, these will be described in detail.

(A) Organic polymer The organic polymer (A) of the present invention has a stain resistance imparting group and a group capable of being polymerized by irradiation with an active energy ray.
Here, preferable examples of the active energy rays include ultraviolet rays, electron beams, α rays, β rays, and γ rays. Accordingly, “polymerization by irradiation with active energy rays” in the present invention includes photoradical polymerization and photocationic polymerization.
The organic polymer (A) of the present invention can be polymerized by, for example, irradiating an active energy ray with a radical polymerizable monomer having a stain resistance imparting group (hereinafter sometimes referred to as (A-1)). A polymer obtained by polymerizing a radically polymerizable monomer having a group (hereinafter sometimes referred to as (A-2)), or a radical copolymerization of these monomers with the above (A-1) and (A-2) A polymer obtained by polymerizing a polymerizable radical polymerizable monomer (A-3) (hereinafter sometimes referred to as (A-3)) can be preferably employed.
Hereinafter, these monomers will be described.

(A-1) Radical polymerizable monomer having stain resistance imparting group The stain resistance imparting group is preferably composed of an organo (poly) siloxane group, an organic fluorine compound group, and a linear alkyl group having 12 or more carbon atoms. It is at least one member of the group, and more preferably a perfluoroalkyl group, a perfluoroalkylene group, a polysiloxane group, or a linear alkyl group having 12 or more carbon atoms. These may be only one type or may include a plurality of types.
Specific examples of (A-1) include perfluorooctylethyl methacrylate, perfluorodecylethyl methacrylate, pentafluoroethyl methacrylate, methoxyethyl perfluoroethylene ethyl acrylate, dimercaptopropylpolydimethylsiloxane, polydimethylsiloxysilylpropyl methacrylate, Lauryl acrylate, lauryl methacrylate, myristyl acrylate, myristyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate and the like are preferable. Of course, it is not limited to these.
The antifouling group in (A-1) is provided on the side chain and / or the main chain, and is preferably a side chain. However, when it has a polydimethylsiloxane structure, it may be preferable that it is provided in the main chain.

(A-2) Radical polymerizable monomer having a group capable of being polymerized by irradiating active energy rays. Polymerization by irradiating active energy rays as used in the present invention is particularly defined as long as it is polymerized by light. However, it is preferably a group capable of photocationic polymerization or a group capable of photoradical polymerization.
(A-2-1) Group capable of photocationic polymerization As a group capable of photocationic polymerization, for example, a ring-opening polymerizable group, in particular, an epoxy group or an oxetane group is preferable. These may be only one type or may include a plurality of types. (A-2-1) is more preferably a radically polymerizable monomer such as an acrylic ester, methacrylic ester, acrylamide or methacrylamide having an epoxy group and / or an oxetane group in the side chain. Specific examples of (A-2-1) include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl. Methyl methacrylate, 1-methyloxatanyloxymethyl acrylate, 1-methyloxetanyloxymethyl methacrylate and the like are preferable. Of course, it is not limited to these.
The group capable of photocationic polymerization in (A-2-1) is provided in the side chain and / or the main chain, and is preferably a side chain.

(A-2-2) The group capable of radical photopolymerization is introduced, for example, by the following method.
(1) After radical polymerization of a radically polymerizable monomer having a ring-opening polymerizable group in the side chain, ring opening of the carboxylic acid having a radically polymerizable group such as acrylic acid or methacrylic acid and the ring-opening polymerizable group Introducing by addition reaction;
Here, examples of the radical polymerizable monomer having a ring-opening polymerizable group in the side chain include acrylic acid ester, methacrylic acid ester, acrylamide, and methacrylamide having an epoxy group or oxetane group in the side chain. Specific examples include those exemplified in the above (A-2-1).
(2) After radical polymerization of a radical polymerizable monomer having a functional group that can easily react with an isocyanate group, such as an OH group, in a side chain, a compound having an NCO group and a radical polymerizable functional group is reacted. How to introduce;
Here, examples of the radical polymerizable monomer having an OH group in the side chain include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like. Is not to be done.
In addition, as a compound having an NCO group and a radical polymerizable functional group at the same time, β-isocyanate ethyl (meth) acrylate (methacrylate is available from Showa Denko under the trade name of Karenz MOI) or an OH group (meta ) A compound in which acrylates and one NCO group of diisocyanate (for example, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), etc.) are connected by a urethane bond can be exemplified. .

(A-3) Copolymerizable radical polymerizable monomer The radical polymerizable monomer copolymerizable with the above (A-1) and (A-2) (hereinafter sometimes referred to as (A-3)) Preferably, it has a low reactivity with the epoxy group and does not decrease the stability of the produced polymer, or has a rigid skeleton and does not decrease the hardness. (A-3) is more preferably an acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, or the like having a C 1-4 alkyl group or a cycloalkyl group in the side chain, or a C 1-4 carbon atom. It is a radically polymerizable monomer such as styrenes which may be substituted with an alkyl group or an alkenyl group. Specifically, styrene and its lower (1 to 4 carbon) alkyl group or alkenyl group-substituted derivatives, alkyl (meth) acrylates having 1 to 8 carbon atoms, alkyl (meth) acrylamides, (5 to 20 carbon atoms ( Preference is given to cycloalkyl (meth) acrylates having a poly) cycloalkyl side chain, (meth) acrylamides and the like.

  In the copolymerization, a preferable solvent may be added to the extent that the uniformity of the reaction system is not impaired in order to improve the uniformity. Examples of such solvents include ketone solvents such as acetone and methyl ethyl ketone (MEK), alcohol solvents such as ethanol and methanol, isopropyl alcohol (IPA) and isobutanol, ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether, Preferred examples include ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate, aromatic hydrocarbon solvents such as toluene, and water.

The method for mixing and dissolving the polymerization component and the solvent is not particularly limited. For example, it is preferable to start the polymerization by adding a radical polymerization initiator within a certain time (preferably within 3 hours) after mixing. As the radical polymerization initiator, known initiators generally used for radical polymerization can be used, and organic peroxides such as benzoyl peroxide and di-t-butyl peroxide, 2,2′-azobisbutyl Preferred examples include azo compounds such as rhonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile).
The total concentration of the monomers (including the radical polymerization initiator) in the polymerization solution is preferably 10 to 60% by weight, and the polymerization initiator is preferably 0.1 to 10% by weight based on the monomer mixture. More preferably, 0.2 to 2% by weight is used.
The preferred polymerization temperature varies depending on the radical polymerization initiator used, but the polymerization temperature is 20 to 150 ° C., and the polymerization time is 1 to 72 hours.

Each component is preferably contained in the following range.
(A-1): 1 to 40% by weight, more preferably 1 to 30% by weight
(A-2): 1 to 60% by weight, more preferably 5 to 50% by weight
(A-3): 0 to 80% by weight, more preferably 10 to 80% by weight
(However, the sum of (A-1) to (A-3) is within 100% by weight)
(A-1) By making a component into 40 weight% or less, both stain resistance and hardness can be maintained more effectively. On the other hand, by setting it to 1% by weight or more, better contamination resistance can be maintained.
Even when the component (A-2) is 60% by weight or more, sufficient hardness is obtained, but no significant improvement is observed. On the other hand, when the content is 1% by weight or more, the effect of increasing the hardness by the active energy ray becomes more remarkable, which is preferable.

Production method of organic-inorganic composite (A) (B) For the production of organic-inorganic composite (A) (B) employed in the present invention, for example, a silane coupling agent (B-1) having a mercapto group is used. Can be manufactured. More specifically, the following two methods are considered as preferable methods.
(1) During the polymerization of (A), the inorganic oxide fine particles (B) are first hydrolyzed and condensed in the presence of a silane coupling agent (B-1) having a mercapto group, and in the presence of this condensate. , (A) is polymerized to obtain an organic-inorganic composite in which (A) is bonded to (B) via an —O—Si—R— bond.
(2) Polymerization of (A) is carried out in the presence of a silane coupling agent having a mercapto group, and an alkoxysilyl group is introduced into one end of (A). Next, the polymer and inorganic oxide fine particles are hydrolyzed and condensed to obtain an organic-inorganic composite in which (A) is bonded to (B) via an —O—Si—R— bond.

(B-1) Silane coupling agent having a mercapto group Examples of the silane coupling agent having a mercapto group include trimethoxysilylpropyl mercaptan (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803, and Toray Dow Corning Silicon Co., Ltd., SH6062). Can be illustrated.

(B-2) Inorganic oxide fine particles The inorganic oxide fine particles (B-2) are not particularly limited as long as they do not depart from the spirit of the present invention, but silicon, aluminum, zirconium, titanium, zinc, lead, germanium, indium, Preferred are oxides of tin, antimony, cerium, lithium, or composite oxides thereof. Specifically, oxides of silicon (silica), oxides of aluminum (alumina), composite oxides of silicon-aluminum, zirconium Main components are oxide (zirconia), titanium oxide (titania), zinc oxide, tin oxide, antimony-doped tin oxide, indium-tin composite oxide (ITO), cerium oxide, silica-lithium oxide composite oxide, etc. Can be mentioned. Among these, those containing silica (colloidal silica) as a main component are particularly preferable.
In addition, for example, “having colloidal silica as a main component” is intended to include being composed only of colloidal silica.

The shape of the inorganic oxide fine particles is preferably spherical, hollow, porous, rod-like, fibrous or plate-like, or indefinite, and more preferably spherical. The term “spherical” as used in the present invention is intended to include not only exact spheres but also substantially spherical ones.
The primary particle diameter of the inorganic oxide fine particles is preferably 1 to 100 nm. By making the primary particle diameter 1 nm or more, it is more effective for mechanical properties, and by making it 100 nm or less, secondary aggregation is more effectively prevented, and loss of transparency is more effectively prevented. Can do.
The inorganic oxide fine particles of the present invention can be obtained in a dry powder state or dissolved or dispersed in water or an organic solvent. A sol dissolved or dispersed in water or an organic solvent (hereinafter sometimes referred to as an inorganic oxide fine particle sol) is preferable because it exhibits excellent dispersibility.

Specifically, an aqueous silica sol dissolved or dispersed in water, an organic silica sol having an OH group or an organosilica sol dissolved or dispersed in a polar organic solvent having a ketone group is preferably used as a main component.
Examples of the aqueous silica sol include basic aqueous silica sol (manufactured by Nissan Chemical Industries, Ltd., ST-20), acidic aqueous silica sol (manufactured by Nissan Chemical Industries, Ltd., ST-O), weakly acidic aqueous silica / alumina sol ( Preferred examples include Nissan Chemical Industries, Ltd. (ST-AK) and basic silica / lithium oxide sol (Nissan Chemical Industries, Ltd., lithium silicate).
Further, as the organosilica sol, IPA-dispersed organosilica sol (manufactured by Nissan Chemical Industries, IPA-ST), MEK-dispersed organosilica sol (manufactured by Nissan Chemical Industries, Ltd., MEK-ST) and MIBK-dispersed organosilica sol (Nissan Chemical) As industrial examples, MIBK-ST) manufactured by Kogyo Co., Ltd., and a sol (for example, PGM-dispersed organosilica sol) obtained by using these as a raw material and replacing with an organic solvent having another OH group can be given.

Examples of the organic solvent include methanol, isopropanol, n-butanol, isobutanol, ethylene glycol, ethyl cellosolve, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide and xylene, and these A mixed solvent is mentioned.
The solid content in the dispersion is preferably 5 to 50% by weight and more preferably 10 to 40% by weight from the viewpoint of easy handling and availability.

(B-3) Specific manufacturing method (1)
The bond between the inorganic oxide fine particles (B-2) and the silane coupling agent (B-1) having a mercapto group can be achieved by various methods generally used in the production of this type of compound. Basically, a method is generally used in which the alkoxysilyl group of (B-1) is hydrolyzed to form a silanol group, which is then subjected to a condensation reaction with the alkoxy group and hydroxy group on the surface of the inorganic oxide fine particles. is there.

The water used is used as long as the performance of the membrane and the stability of the coating solution are not impaired. The amount of water added may be an amount equal to or greater than the amount (B-1) that can be hydrolyzed by 100% as a theoretical amount, preferably 100-300% equivalent, more preferably 100-200% equivalent. .
Examples of the water used include distilled water, ion exchange water, industrial water and soft water.

  Furthermore, an acid or alkali, or other suitable compound may be added as a catalyst in order to accelerate this hydrolysis condensation reaction. Any of these may be used as long as the performance of the film is not impaired and the performance of the coating solution is not impaired. For example, as an acid catalyst, hydrogen chloride solution, phosphoric acid solution and inorganic acid such as boric acid, citric acid, maleic acid, acetic acid and organic acid such as paratoluenesulfonic acid, as alkaline catalyst alcoholic potassium hydroxide, ammonia, Examples thereof include trialkylamines and heterocyclic-containing amines such as dimethylaminopyridine. In addition, metal acetylacetone complexes such as aluminum triacetylacetonate are also effective. These amounts are preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the silane compound.

  The reaction is preferably 20 to 100 ° C., 1 hour to 100 hours (more preferably 20 ° C. to 25 ° C., 4 hours or more), followed by heating at 40 to 70 ° C. for 1 to 10 hours to advance the reaction. . In order to suppress side reactions, the reaction system may be diluted with a solvent. The solvent used is preferably one that is compatible with the water or catalyst used, for example, alcohols such as methanol, ethanol, isopropanol and isobutanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, etc. And hydroxyl group-containing ethers such as propylene glycol monomethyl ether.

  The weight ratio of the inorganic oxide fine particles (solid content) to the silane compound is preferably 100 / 0.1 to 100/10, and more preferably 100/1 to 100/5. By setting it within such a range, an appropriate amount of functional groups can be introduced into the inorganic oxide fine particles (B-2), which is preferable.

  Next, an organic-inorganic composite (A) (B) is obtained by copolymerizing the component which comprises (A) in presence of the modified inorganic oxide fine particle obtained by the said method.

  Under the present circumstances, the weight ratio of the component which comprises (A), and (B-1) is 99.5 / 0.5-90 / 10, Preferably it is 99 / 1-97 / 3. By setting it to 0.5 or more, the bond of (A) to (B) becomes more sufficient. On the other hand, by setting it to 10 or less, polymerization termination due to chain transfer to a mercapto group occurs more than necessary, and it is possible to more effectively prevent a component having a number average molecular weight of less than 1000 as the component (A). .

  Other conditions (solvent for improving uniformity, mixing / dissolving method of polymerization component and solvent, etc.) may be carried out in accordance with the description of (A-3) copolymerizable radical polymerizable monomer described above. it can.

(B-4) Specific manufacturing method (2)
In the presence of a silane coupling agent (B-1) having a mercapto group, the component constituting (A) is copolymerized to introduce an alkoxysilyl group at one end. Next, this polymer and inorganic oxide fine particles (B-2) are hydrolyzed and condensed to obtain organic / inorganic composites (A) and (B).

When the component constituting (A) is copolymerized in the presence of (B-1), the weight ratio of the component constituting (A) and (B-1) is 99.5 / 0.5 to 90/10, preferably 99/1 to 97/3. By setting it to 0.5 or more, the bond of (A) to the inorganic oxide fine particles becomes more sufficient in the subsequent reaction, which is preferable. On the other hand, by making it 10 or less, it is possible to more effectively prevent the polymerization termination due to chain transfer to the mercapto group more than necessary, and more effectively preventing the component (A) having a number average molecular weight of less than 1000 from increasing. Can do.

  Other conditions (solvent for improving uniformity, mixing / dissolving method of polymerization component and solvent, etc.) may be carried out in accordance with the description of (A-3) copolymerizable radical polymerizable monomer described above. it can.

  Next, the inorganic / organic composite particles (A) and (B) are obtained by hydrolyzing and condensing the inorganic oxide fine particles in the presence of the polymer of the one-end alkoxysilyl group thus obtained.

Detailed conditions for hydrolysis and condensation (water used, catalyst, reaction conditions, weight ratio, etc.)
Can be carried out according to the description in the above-mentioned (B-2) inorganic oxide fine particles.

  In the production of the organic-inorganic composite (A) (B) used in the present invention, the following organic-inorganic composite (A ′) (B) may be used.

  The organic-inorganic composite (A ′) (B) used in the present invention can be produced, for example, using a silane coupling agent (B-5) having a (meth) acryloyl group.

（式（１）中、Ｘ及びＹは、それぞれ独立に、酸素原子、イオウ原子またはイミノ基を表す）。 (B-5) Silane coupling agent having (meth) acryloyl group On the surface of the inorganic oxide fine particles, -O-Si-R- bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms) In order to bind a group having a (meth) acryloyl group via (more preferably —O—Si—R—S— bond), a silane coupling agent having a (meth) acryloyl group (hereinafter referred to as (B −5)) may be used.
A preferred example of such (B-5) is a silane coupling agent having a molecular weight of 300 or more and containing at least one acryloyl group or methacryloyl group as a radical polymerizable functional group. The number of acryloyl groups or methacryloyl groups is not particularly limited, but preferably 1 to 5 polymerizable functional groups per molecule. Further, the position is not particularly limited, but it is preferably at the end of the molecule. In addition, (B-5) is more preferably an organic compound having a functional group represented by the following formula (1) at the same time.
Formula (1)

(In formula (1), X and Y each independently represents an oxygen atom, a sulfur atom or an imino group).

  The functional group represented by the formula (1) has an effect of increasing mechanical strength by generating excessive cohesive force due to hydrogen bonding between molecules, and improving the adhesion to a substrate, heat resistance, and the like. It also functions as a spacer between the surface of the inorganic oxide fine particles and the radical polymerizable functional group. Specific examples include -OCONH-, -SCON-, -SCSNH-, -OCSNH-, -NHCONH-, and -NHCSNH- (hereinafter, these may be collectively referred to as Formula (2)). it can. Of these groups, —OCONH— and —SCONH— are particularly preferred from the viewpoints of thermal stability and ease of synthesis.

  (B-5) may be an organic compound having a thioether group at the same time. A thioether group is also preferable because it acts as a spacer between the silica surface and a radical polymerizable functional group or a specific polar functional group, and has an effect of suppressing excessive aggregation.

  As the functional group of the silane coupling agent that can bind to the inorganic oxide fine particles, an alkoxysilyl group that is a group capable of generating a silanol group is particularly preferable. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. Among them, a trialkoxysilyl group of a lower alcohol such as a trimethoxysilyl group or a triethoxysilyl group is reactive. This is particularly preferable. The position of these groups in the molecule is preferably at the end of the molecule opposite to the (meth) acryloyl group. Moreover, it is preferable that the number of groups in 1 molecule is 1-3, and it is more preferable that it is one.

The silanol group or silanol group-generating unit is a generated unit that binds to the inorganic oxide fine particles by a condensation reaction or a condensation reaction that occurs following hydrolysis. Some preferred examples of such compounds are:
1) a compound in which an OH group of a (meth) acrylate compound having an OH group and an NCO group of a trialkoxysilane having an NCO group are bonded via -OCONH-
2) An SH group of a trialkoxysilane compound having an SH group and one NCO group of diisocyanate are bonded via -NHCOS-, and a (meth) acrylate compound having an OH group is allowed to act on the remaining NCO group, A compound bonded via NHCOO-,
3) a compound in which an NCO group of a (meth) acrylate compound having an NCO group and an SH group of a trialkoxysilane having an SH group are bonded via —NHCOS—,
4) A compound containing two or more (meth) acryloyl groups in the molecule and a trialkoxysilane having an SH group are formed by a Michael addition reaction to an unsaturated group ((meth) acryloyl group) of the SH group. And a compound obtained by reacting a mono (meth) acrylic acid ester of an α, ω-hydroxy-terminated polyalkylene glycol with a silane coupling agent having an NCO group,
Needless to say, the present invention is not limited to these examples.

  Examples of the (meth) acrylate having an OH group include mono (meth) acrylate (such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate), di (meth) acrylate (glycerin di (meth) acrylate and Trimethylolpropane di (meth) acrylate) and tri-poly (meth) acrylate (pentaerythritol triacrylate, dipentaerythritol tri-pentaacrylate, and ditrimethylolpropane triacrylate) are preferable.

  Examples of trialkoxysilane compounds having an NCO group include triethoxysilylpropyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd., KBE9007), trimethoxysilylpropyl isocyanate, and trimethoxysilylpropyl mercaptan (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803, and Toray Industries, Inc.). A trialkoxysilylalkylmercaptan such as Dow Corning Silicon, SH6062 and the like and one NCO group of diisocyanate (isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI), etc.) Examples thereof include compounds bonded via a urethane bond.

  The production method of -OCONH- by the reaction of OH group and NCO group is blended in such a ratio that each compound NCO group / OH group ≦ 1, and mixed and stirred at 60 to 100 ° C. for 1 hour to 20 hours. can get. In this reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol and phenothiazine in order to prevent polymerization due to the acrylic group during the reaction. The amount is preferably 0.01 to 1%, more preferably 0.05 to 0.5% by weight, based on the reaction mixture. In order to accelerate the reaction, for example, a known reaction catalyst such as di-n-butyltin dilaurate and diazabicyclooctane (DABCO) may be added. Furthermore, this reaction is carried out, for example, with a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an ether solvent such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, a carboxylic acid ester solvent such as ethyl acetate and butyl acetate, and xylene and toluene. In a solvent that does not contain a group capable of reacting with an isocyanate group, such as an aromatic hydrocarbon solvent, or in the presence of a polyfunctional acrylate having three or more (meth) acryloyl groups in the molecule. Can do.

  As the (meth) acrylate compound having an NCO group, β-isocyanate ethyl (meth) acrylate (manufactured by Showa Denko, Karenz MOI), or (meth) acrylates having an OH group (manufactured by Showa Denko, Karenz MOI), Examples thereof include compounds in which one NCO group of diisocyanate (isophorone diisocyanate, hexamethylene diisocyanate, MDI, TDI, etc.) is bonded via a urethane bond.

  Examples of the trialkoxysilane compound having an SH group include trimethoxysilylpropyl mercaptan (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803, and Toray Dow Corning Silicon Co., Ltd., SH6062) and the like.

The production method of -NHCOS- by the reaction of the NCO group and the SH group can be performed in the same manner as the production of -NHCOO- by the reaction of the NCO group and OH group.
Examples of mono (meth) acrylic acid ester compounds of α, ω-hydroxy-terminated polyalkylene glycol include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, and poly (ethylene / Propylene) glycol mono (meth) acrylate and poly (ethylene / tetramethylene) glycol mono (meth) acrylate.

  The reaction of a mono (meth) acrylate compound of an α, ω-hydroxy-terminated polyalkylene glycol and a trialkoxysilyl compound having an NCO group is carried out in the same manner as in the production of —NHCOO— by the reaction of an NCO group and an OH group. be able to.

(B-6) Specific production method (1)
Bonding of the inorganic oxide fine particles (B-2) and the silane coupling agent (B-5) having a (meth) acryloyl group is achieved by various methods generally used in the production of this type of compound. Is possible. Basically, it is common to hydrolyze the alkoxysilyl group of (B-5) to form a silanol group and to combine it by a condensation reaction with the alkoxy group and hydroxy group on the surface of the inorganic oxide fine particles. .
About reaction and a coupling | bonding of (B-5) and inorganic oxide microparticles | fine-particles, it can be achieved by the various method generally used in this kind of compound production | generation. Basically, a method is generally used in which the alkoxysilyl group of (B-5) is hydrolyzed to form a silanol group and then subjected to a hydrolytic condensation reaction with the alkoxy group and / or hydroxy group on the surface of the inorganic oxide fine particles to bond them. Is.

Detailed conditions for hydrolysis and condensation (water used, catalyst, reaction conditions, weight ratio, etc.)
Can be carried out according to the description in the above-mentioned (B-2) inorganic oxide fine particles.

  Apart from the above, among the components capable of synthesizing the above (B-5), an alkoxysilyl compound having a functional group capable of generating a bonding group represented by the formula (1) or the formula (2) in advance is first an inorganic oxide. After reacting with the fine particle sol, another compound may be reacted, and a polymerizable unsaturated group and a bonding group represented by formula (1) or formula (2) may be introduced into the compound. Of the formula (1), a trialkoxysilane compound having an SH group as a compound having an alkoxysilyl group can be reacted with the inorganic oxide fine particles (B-2) in advance.

  For example, a trialkoxysilane having an SH group is reacted with the inorganic oxide fine particles (B-2), and then the SH group is reacted with a diisocyanate compound, and one NCO group is used to connect with an NHCOS bond, and the remaining NCO A structure similar to that of the previous method can be obtained by a method in which a (meth) acrylate compound having an OH group is allowed to act and the NHCOO bond is used for connection.

  In addition, a trialkoxysilane having an SH group is reacted with (B-2) and then reacted with a (meth) acrylate compound and / or a (meth) acrylamide compound having an NCO group, whereby the same structure as the previous method is obtained. Can be obtained.

  In this case, the reaction ratio between the trialkoxysilane having an SH group and (B-2) is preferably 90/10 to 5/95, more preferably 80/20 to 10/90 in terms of weight ratio. By setting it in such a range, the surface of the inorganic oxide can be more sufficiently protected, and further, the dispersion state due to polymerization and crosslinking of the alkoxysilane itself can be further stabilized, and an increase in viscosity can be prevented. preferable. Further, the molecular weight of the trialkoxysilane having an SH group is desirably 300 or more. By setting it to 300 or more, the effect of generating a protective colloid becomes higher, and aggregation and gelation due to condensation, crosslinking, etc. of the trialkoxysilane itself having an SH group can be more effectively suppressed, which is preferable.

  The reaction is preferably performed at room temperature to 100 ° C. for 1 hour to 100 hours, more preferably at room temperature for 4 hours or more, followed by heating at room temperature to 70 ° C. for 1 to 10 hours. In order to suppress side reactions, the reaction system may be diluted with a solvent. The solvent used is preferably a hydrolyzate silane alkoxide, water or a catalyst compatible with the catalyst, for example, alcohols such as methanol, ethanol, isopropanol and isobutanol, acetone, methyl ethyl ketone and methyl isobutyl ketone. Mention may be made of ketones, ethers such as tetrahydrofuran and dioxane, and hydroxyl group-containing ethers such as propylene glycol monomethyl ether.

  Further, a part of (B-5) (less than 50% by weight) may be replaced with another silane coupling agent. As other silane coupling agents, in addition to various known commercially available silane coupling agents, a silane coupling agent having a polyalkylene glycol structure that does not have a radical polymerizable functional group, a COOH group, or a COOR ′ group (R ′ is A silane coupling agent having an alicyclic structure, a silane coupling agent obtained by reaction of a bulky alcohol having a branched structure and an alkoxysilyl group having an NCO group, etc. Can be illustrated.

(B-7) Specific production method (2)
The inorganic oxide fine particles (B) have a side chain having a functional group whose side chain is a silyl ether group represented by the following structural formula. It is also possible to adopt the group shown in
-O-Si-R-S-P
However, R is an alkylene group which may have a branch having 2 to 10 carbon atoms, and P is a polymer unit having at least one (meth) acryloyl group.

The organic / inorganic composite (A ′) (B) having such a group is preferably either of the following two.
(1) In polymerizing a monomer having an epoxy group and one radical polymerizable group, the inorganic oxide fine particles (B-2) are first hydrolyzed in the presence of a silane coupling agent having a mercapto group. Condensation is performed and polymerization is performed in the presence of the condensate to produce an organic-inorganic composite in which the polymer is bonded to the inorganic oxide fine particles through —O—Si—R— bonds. Subsequently, the compound which has a carboxyl group and a (meth) acryloyl group is added to the epoxy group of this polymer, and it is set as the desired organic-inorganic composite (A ') (B).
(2) A monomer having an epoxy group and one radical polymerizable group is polymerized in the presence of a silane coupling agent having a mercapto group, and an alkoxysilyl group is introduced into one end of the polymer. Next, a compound having a carboxyl group and a (meth) acryloyl group is added to the epoxy group of this polymer, and finally, the terminal alkoxysilyl group of this polymer and the inorganic oxide fine particles are hydrolyzed and condensed to obtain the desired organic-inorganic composite ( A ′) and (B).

  Regarding other conditions (detailed conditions for polymerization and hydrolysis condensation), etc., the description of the above-mentioned (B-1) silane coupling agent having a mercapto group, and (A-3) a copolymerizable radical polymerizable monomer Can be carried out in accordance with the description. However, the monomer used for polymerization in this case needs to be changed to a monomer having an epoxy group and one radical polymerizable group. Specific examples of each monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like. If necessary, the monomer having an epoxy group can be radically copolymerized with other monomers. Other monomers are not particularly limited as long as they do not react with epoxy groups.

The monomer (the monomer having an epoxy group and other monomer used in combination as required) and the inorganic oxide fine particles (B-2) are reacted at a weight ratio of 30/70 to 95/5. The polymerization reaction is more preferably carried out at 50/50 to 90/10. When the weight ratio of the inorganic component is 70 or less, the inorganic oxide fine particles are more stable, and when the weight ratio is 5 or more, higher wear resistance is obtained.
This radical polymerization reaction is performed using a normal radical polymerization initiator in a solvent. Solvents include alcohols (ethanol, isopropanol, isobutanol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohols having alkoxy groups (methoxyethanol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc.) ), Ethers (ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.), ether esters (propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, etc.), aromatic hydrocarbons (toluene, xylene, etc.), esters (ethyl acetate, Examples thereof include propyl acetate and the like, and these can be used in combination.

  Here, a method for adding a compound having a carboxyl group and a (meth) acryloyl group to the epoxy group of the polymer, which has not been described in detail, will be described in detail.

  Examples of the compound having a carboxyl group and a (meth) acryloyl group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, pentaerythritol tri ( Adducts of acid anhydrides such as meth) acrylate and succinic anhydride, phthalic anhydride and hexahydrophthalic anhydride, acid anhydrides such as dipentaerythritol penta (meth) acrylate and succinic anhydride, phthalic anhydride and hexahydrophthalic anhydride The adduct of a thing can be mentioned. In the third step, the epoxy group of the polymer reacts with the carboxyl group of the (meth) acryloyl group introduction reagent. The polymer and the (meth) acryloyl group-introducing reagent are preferably mixed at a ratio of epoxy group / carboxyl group of 1 or more, more preferably 1-10.

  The reaction is preferably carried out at 50 to 110 ° C. for 3 to 50 hours. In this reaction, known catalysts such as triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride, and triphenylphosphine can be used to accelerate the reaction. The amount used is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, based on the reaction mixture.

  In this reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol and phenothiazine in order to prevent radical polymerization due to the (meth) acryloyl group. The amount of the polymerization inhibitor used is preferably 0.01 to 1% by weight, more preferably 0.05 to 5% by weight, based on the reaction mixture.

  The solvent used may be various reaction solvents used in each production step of the inorganic oxide fine particles, for example, a dispersion medium of inorganic oxide fine particles used in the first step, Moreover, the solvent used for reaction of the said 2nd process may be sufficient. Furthermore, after manufacturing the said inorganic oxide microparticles | fine-particles, the solvent used for viscosity adjustment may be sufficient.

  The content of the inorganic oxide fine particles (B-2) in the stain resistance imparting agent of the present invention is not particularly defined unless it deviates from the gist of the present invention, but is used as a composition requiring particularly high hardness. In some cases, the preferred composition (B-2) / (A) has a weight ratio of 99.5 / 0.5 to 80/20. By making (A) 20 or less, higher hardness can be maintained, which is preferable. A more preferable range is 99/1 to 85/15.

(C) Cationic polymerizable photoinitiator The cationic polymerizable photoinitiator (C) is not particularly limited, but is preferably an aromatic iodonium salt compound or an aromatic sulfonium salt compound. It is. (C) is specifically a diaryl iodonium salt type or a triarylsulfonium salt type, and the counter ion is preferably PF ₆ , SbF ₅ , AsF ₆ , BPh ₄ , CF ₃ OSO ₂ or the like. . The content of (C) is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of (A).
Further, in order to further secure curability, amines (such as triethanolamine), phosphines (such as tributylphosphine), and thioxanthones may be used in combination. In this case, these compounds are preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of (A).

(D) Radical-polymerizable photoinitiator Irradiation with radical-polymerizable active energy rays and a wide variety of known polymerization initiators can be used. Preferably, an alkylphenone type compound (α-hydroxyacetophenone, α- Aminoacetophenone series, benzyl ketal series, etc.), acylphosphine oxide type compounds, oxime ester type compounds, oxyphenyl acetates, benzoin ethers, ketone / amine compounds and the like. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2 , 4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like are preferable. By irradiating these active energy rays, two or more kinds of polymerization initiators can be appropriately used in combination.
The radical polymerizable photoinitiator (D) is preferably 10% by weight or less, more preferably 1 to 5% by weight of the sum of the polymerizable components (A), (B) and (A ′) and (B).

  When 20% by weight or more of the component (D) is used as the radical polymerizable photoinitiator (D), polymerization inhibition due to oxygen is further reduced, and surface curability / thin film curability is improved. Seen and may be particularly preferred. Illustrative examples are: a) α-aminoacetophenone initiators (eg 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, etc.), b) oxime ester initiators (eg, Ciba Specialty Chemicals, Irgacure OXE-01, etc.), c) α-hydroxyketone initiators Agent + benzophenone sensitizer (for example, 1-hydroxycyclohexyl phenyl ketone + Michler's ketone, etc.).

(E) Organic (meth) acrylate compound and / or (meth) acrylamide compound As the organic (meth) acrylate compound and / or (meth) acrylamide compound, polyfunctional (meth) having three or more acryloyl groups in one molecule Any of an acrylate compound, an organic (meth) acrylate compound having 1 to 2 (meth) acryl groups in one molecule, and an organic and (meth) acrylamide compound is preferable.
A polyfunctional (meth) acrylate compound having 3 or more acryloyl groups in one molecule is preferable because it can further increase the hardness.
An organic (meth) acrylate compound or organic (meth) acrylamide compound having 1 to 2 (meth) acrylic groups in one molecule is preferable for adjusting the viscosity and other physical properties.

Examples of the (meth) acrylate compound having one (meth) acryl group in one molecule include alicyclic (meth) alkyl (meth) acrylates such as butyl methacrylate and stearyl acrylate, cyclohexyl acrylate and isobornyl methacrylate, and the like. Preferred are acrylate, (meth) acrylate having an aromatic ring, (meth) acrylate having a hydroxy group, (meth) acrylate having a polyalkylene glycol chain, alkyl (meth) acrylate such as butyl methacrylate and stearyl acrylate, cyclohexyl acrylate and iso More preferred are alicyclic (meth) acrylates such as bornyl methacrylate. Of course, nothing other than these is not excluded.
Examples of (meth) acrylate compounds having two (meth) acrylic groups in one molecule include poly (alkylenes) such as di (meth) acrylates of aliphatic or alicyclic diols such as hexanediol diacrylate, and polyethylene glycol diacrylate. Glycol di (meth) acrylate and the like are preferable. Of course, nothing other than these is not excluded.

Examples of (meth) acrylamide compounds having 1 to 2 (meth) acrylic groups in one molecule include alkyl (meth) acrylamides such as ethyl acrylamide and aminoalkyl-containing (meth) such as N, N-dimethylaminopropyl acrylamide. Acrylamide and the like are preferable. Of course, nothing other than these is not excluded.
Examples of polyfunctional (meth) acrylate compounds having three or more (meth) acryloyl groups in one molecule include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ditrimethylolpropanetetra. Preferred are acrylates, polyester acrylates, polyfunctional urethane acrylates, polyepoxy acrylates, and the like. Of course, nothing other than these is not excluded.
(E) is preferably 90% by weight or less, more preferably 10 to 80% by weight, based on the sum of the polymerizable components (A), (B), and (A ′) and (B).

(F) Polymer having radical polymerizable group The polymer having a radical polymerizable group is preferably a (meth) acrylate polymer having a radical polymerizable group such as acryloyl group or methacryloyl group in the side chain, A copolymer of such a polymer and another radical polymer monomer such as styrene. Specifically, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate were polymerized as main components. A polymer obtained by adding (meth) acrylic acid to a polymer and having a (meth) acryloyl group in the side chain is preferred. Of course, nothing other than these is not excluded.
(F) is preferably 60% by weight or less, more preferably 0 to 40% by weight of the sum of the polymerizable components (A), (B) and (A ′) and (B).

(G) Organic epoxy compound As an organic epoxy compound, a compound having two or more epoxy groups in one molecule, a compound having one epoxy group in one molecule, an epoxy group and a (meth) acryloyl group in one molecule. The compound which it has simultaneously is preferable.
In order to further increase the hardness, a compound having two or more epoxy groups in one molecule is preferable, and in order to adjust viscosity and other physical properties, a compound having one epoxy group in one molecule is preferable.
Compounds having two or more epoxy groups in one molecule include diepoxy compounds of bisphenols and their hydrides, novolac type epoxy compounds and their hydrides, di-polyepoxy compounds of aromatic amines, and other bifunctional compounds. Although a polyfunctional epoxy compound is mentioned as a preferable example, it is not limited to these.
Preferable examples of the compound having one epoxy group in one molecule include phenyl glycidyl ether and butyl glycidyl ether, but are not limited thereto.

Polymers having two or more epoxy groups in one molecule include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4 A polymer obtained by polymerizing epoxy cyclohexyl methyl methacrylate as a main component can be given as a preferred example, but the polymer is not limited thereto.
Examples of the compound having an epoxy group and a (meth) acryloyl group in one molecule include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3, Preferred examples include 4-epoxycyclohexylmethyl methacrylate or a partial (meth) acrylic acid adduct of a polymer obtained by polymerizing these as a main component, but are not limited thereto.
(F) is preferably 30% by weight or less, more preferably 0 to 20% by weight, based on the sum of the polymerizable components (A), (B), and (A ′) and (B).

(H) Organic Oxetane Compound As the organic oxetane compound, a series of oxetane compounds available from Toagosei (for example, EXOA and its derivatives, XDO), and an oxetane group described in JP-A-2001-40205, etc. Although the polymer etc. which have in a side chain can be mentioned as a preferable example, it is not limited to these.
(H) is preferably 30% by weight or less, more preferably 0 to 20% by weight, based on the sum of the polymerizable components (A), (B), and (A ′) and (B).

In addition to the above, when the ultraviolet absorber (I) and the hindered amine light stabilizer (J) are added to the stain resistance imparting agent of the present invention for the purpose of imparting various functions, the weather resistance is remarkably improved. May be preferred.
Preferred examples of the ultraviolet absorber (I) include benzotriazole, benzophenone, salicylic acid, cyanoacrylate, and triazine ultraviolet absorbers.
As the hindered amine light stabilizer (J), for example, an N-methyl form such as Sanol LS765 is preferable, but a normal NH form such as LS-770 may be used.
Each preferable blending amount varies depending on the desired weather resistance level. In many cases, 0.5 to 30 parts by weight is preferable with respect to 100 parts by weight of the total of (A) to (H), and 1 to 10 parts by weight. Part is more preferred.

For the purpose of improving the physical properties of the coating film, the stain resistance imparting agent of the present invention includes an antioxidant (for example, a hindered phenol-based, sulfur-based, phosphorus-based antioxidant, etc.), an anti-blocking agent, a slip agent, and a leveling agent. You may mix | blend various additives etc. which are mix | blended with this kind of stain-resistant imparting agents, such as an agent. As a compounding quantity in this case, 0.01 to 2 weight% is preferable.
Furthermore, it is also preferable to use the same solvent as the solvent used in the production of (A-1) for adjusting the viscosity of the stain resistance imparting agent.

  In addition, the stain resistance imparting agent of the present invention further includes inorganic oxide fine particles (preferably inorganic oxide fine particles mainly containing colloidal silica), and —O—Si—R added to the inorganic oxide fine particles. An organic-inorganic composite having an organic component (A ′) having a (meth) acryloyl group bonded via a bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms) (Hereinafter may be referred to as (A ′) (B) complex). Such (A ′) (B) complex can be performed according to the description of the organic-inorganic complex (A) (B). By including such an organic-inorganic composite, the effect of improving hardness and scratch resistance can be obtained. In particular, the organic component having a (meth) acryloyl group of (A ′) has a number average molecular weight of 1000 or more, an organic polymer having a (meth) acryloyl group in the side chain, or a molecular weight of 1000 or less containing a (meth) acryloyl group. A combination such as a group is particularly preferred. The content of the (A ′) (B) complex is 99.5 to 50 parts by weight (more preferably 99 to 80 parts by weight) with respect to the (A) and (B) complex.

Examples of the stain resistance imparting agent of the present invention include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polymethyl methacrylate (PMMA), and methyl methacrylate (MMA) copolymers (for example, modified silicone (MS Resin)), polycarbonate, triacetyl cellulose, acrylonitrile butadiene styrene copolymer (ABS resin), and other plastic substrates. It goes without saying that these substrates may be in the form of molded articles (articles).
Preferable examples of the application method include dip coating, flow coating, spin coating, spray coating, bar coating, gravure coating, roll coating, blade coating, air knife coating, and the like.

A polymerized and cured coating is obtained by irradiating with active energy rays after forming a coating on the substrate by the above coating method by solvent drying. The thickness of the film obtained by coating, polymerization, and curing is not particularly defined, and may be, for example, 5 μm or more, or 2 μm or less. The stain resistance imparting agent of the present invention is extremely significant in that both thinning and thickening are possible. The thickness of the coated film is particularly preferably 0.01 to 50 μm, particularly preferably 2 to 20 μm when the hardness is important, and particularly preferably 0.04 to 2 μm when the hardness is not relatively important.
As the active energy ray irradiation method, ultraviolet rays emitted from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or preferably 20 to 2000 kV are taken out from a particle accelerator. An active energy ray such as electron beam, α ray, β ray, γ ray is irradiated and cured to form a film.
A film cured with such an active energy ray is particularly preferable because of its excellent balance between productivity and physical properties.

The cured product obtained by curing the stain resistance imparting agent of the present invention preferably satisfies the following physical properties.
1) Pencil hardness The stain resistance imparting agent of the present invention is applied to a 100 μm thick PET film with a dry film thickness of 5 μm, and the cured film and the cured film have a pencil hardness of HB or more, more preferably F. The above is preferable. In addition, pencil hardness is 6B, 5B, ... B, HB, F, H, 2H, 3H, ... 9H in an order from a soft thing.
In particular, it is preferable that a stain resistance imparting agent containing an organic-inorganic composite is applied to a 100 μm thick PET film with a dry film thickness of 10 μm, and the pencil hardness of the cured coating film is 3H or more.
2) Warpage amount It is preferable that the stain resistance imparting agent of the present invention is applied to a 100 μm thick PET film with a dry film thickness of 10 μm, and the amount of warpage of the coated film after curing is 10 mm or less. More preferably, it is 2 mm or less.
3) Curability The stain resistance-imparting agent of the present invention is applied to a PET substrate having a thickness of 100 μm with a dry film thickness of 0.5 μm, and curing proceeds until it is completely tack-free with an ultraviolet irradiation amount of 300 mJ / cm ^2. It is preferable to do. Or it is preferable to apply | coat with a dry film thickness of 2 micrometers, and to harden | cure until it becomes tack-free completely by the ultraviolet irradiation amount of 150 cm < ² >.

4) ESCA
The film formed by applying the stain resistance imparting agent of the present invention on a substrate has a content of the stain resistance imparting group at a position 3 nm thick from the surface of the film, so that the contamination resistance imparting group of the entire film is present. The average content is preferably 3 times or more, and more preferably 3.2 to 100 times. Here, the content of the stain resistance-imparting group can be determined, for example, by measurement with an X-ray photoelectron spectroscopic analyzer (hereinafter referred to as ESCA). That is, the number ratio of atoms in the range of 3 nm from the surface can be obtained using ESCA, and the average composition ratio of the stain resistance imparting agent can be obtained by comparison. Here, for example, when a fluorine-based stain resistance imparting group is used, an F / C ratio is obtained. When a silicone stain resistance imparting group is used, an Si / C ratio is obtained, and a long-chain alkyl is obtained. When using the system stain resistance imparting group, it is possible to make a comparison by calculating all the atomic ratios included in detail.
One of the features of the stain resistance-imparting agent of the present invention is that such a constitution can be obtained. As a result, even if the content of the stain-resistance imparting group is 1% by weight, the surface of the coating film is resistant to contamination. This is because the sex-imparting group is efficiently concentrated.

5) Abrasion resistance When the stain resistance imparting agent of the present invention is a film formed by applying the stain resistance imparting agent to a polyethylene terephthalate film having a thickness of 100 μm, it is usually cured in an oxygen concentration atmosphere. Those having wear resistance of 25.0 or less are preferred.

Further, in the stain resistance imparting agent of the present invention, the total amount of the cationic polymerizable photoinitiator (C) and the radical polymerizable photoinitiator (D) is 0 with respect to 100 parts by weight of the (A) (B) composite. 5 to 20 parts by weight (more preferably 1 to 10 parts by weight),
Radical polymerizable organic (meth) acrylate compound and / or radical polymerizable organic (meth) acrylamide compound (E), polymer (F) having radical polymerizable group, organic epoxy compound (G) and organic oxetane compound (H ) Is 0 to 70 parts by weight (more preferably 0 to 30 parts by weight),
The total amount of ultraviolet absorber (I), hindered amine light stabilizer (J), antistatic agent (K), slipperiness imparting agent (L), antifogging imparting agent (M) and peelability imparting agent (N) is 0 to 30 parts by weight (more preferably 0 to 10 parts by weight),
(A ′) (B) The composite is preferably contained in an amount of 99.5 to 50 parts by weight (more preferably 99 to 80 parts by weight) when hardness and scratch resistance are particularly important.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
In the examples, parts and% mean parts by weight and% by weight, respectively.
The evaluation method of the general physical properties of the coating film in Examples etc. is shown below.
(1) Transparency: The haze value was evaluated based on the conditions of JIS K-7105.
(2) Pencil hardness: Using a JIS-compliant pencil hardness system (manufactured by Dazai Equipment Co., Ltd.), the measurement was performed based on the conditions of JIS K-5400, and the hardness was indicated by the hardest pencil number without scratches.
(3) Contact angle to water 0.002 ml of pure water was dropped on the coating film, and the contact angle after 1 minute was measured. The contact angle was measured using a P-type contact angle measuring device (manufactured by Kyowa Science Co., Ltd.) (unit: degree).
(4) Coating film adhesion: Tested by a cross cut method described in JIS K-5400. Here, 100 grids were placed at 1 mm intervals and tested with cellophane tape (manufactured by Nichiban Co., Ltd.). Regarding the evaluation method, the same operation was repeated five times (cellophane tape was always used a new one), and no scratch or peeling occurred. The measurement was evaluated by changing the method to x, otherwise.
(5) Fingerprint wiping property (1-1): The nasal oil was used as a substitute for sebum, the nasal oil was placed on the thumb, and the thumb was pressed vertically against the coating film for 3 seconds to attach a fingerprint to the coating film. The surface of the fingerprint was lightly wiped with a tissue paper (manufacturer: Crecia), and the number of reciprocations until it became visually invisible at a distance of 15 cm was defined as fingerprint wiping property (1-1).
(6) Fingerprint wiping property (1-50): The above-described fingerprint wiping property (1-1) was repeated on the same coating film, and the number of repetitions was 50. In the 50th operation, the surface of the fingerprint was lightly wiped with a tissue paper (manufacturer: Crecia), and the number of reciprocations until it was visually invisible at a distance of 15 cm was defined as fingerprint wiping property (1-1).
If the fingerprint wiping property (1-1) and the fingerprint wiping property (1-50) are the same number of reciprocations, the fingerprint wiping repeatability is excellent.
(7) Fingerprint wiping property (2): The surface of the coating film was rubbed 100 times with an eraser, and then evaluated in the same manner as the fingerprint wiping property (1-1).
(8) Feeling of wiping: The feeling of slipping on the surface when the above-mentioned fingerprint wiping property was performed was evaluated in terms of size. ◯: High slip feeling, Δ: Small slip feeling, x: No slip feeling, evaluated.

Synthesis Example 1: Synthesis of organic-inorganic complex (A11) (B) within the scope of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, perfluorooctylethyltrimethoxysilane 2 g, After adding 0.025 g of aluminum acetylacetonate and stirring until uniform, 1.50 g of pure water was added and stirred at room temperature for 3 hours. After mixing 30 g of perfluorooctylethyl methacrylate, 50 g of methyl methacrylate, 10 g of cyclomer M100 (manufactured by Daicel) and 200 g of MEK, the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. The solid concentration was about 32% (A11) (B).

Synthesis Example 2: Synthesis of organic-inorganic composite (A12) (B) within the scope of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, and aluminum acetylacetonate 0.025 g were added. After stirring until uniform, 1.50 g of pure water was added and stirred at room temperature for 3 hours. This was mixed with 10 g of perfluorooctylethyl methacrylate, 50 g of methyl methacrylate, 30 g of cyclomer M100, and 200 g of MEK, and then the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. The solid concentration was about 32% (A12) (B).

Synthesis Example 3: Synthesis of organic-inorganic composite (A13) (B) within the scope of the present invention MEK-ST111g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3g, and aluminum acetylacetonate 0.025g were added. After stirring until uniform, 1.50 g of pure water was added and stirred at room temperature for 3 hours. After mixing 10 g of perfluorooctylethyl methacrylate, 2 g of α, ω-dimercaptopolydimethylsiloxane (Shin-Etsu Chemical Co., Ltd., X-22-167B), 10 g of methyl methacrylate, 70 g of cyclomer M100, and 200 g of MEK, the internal temperature was changed to nitrogen. The temperature was raised to about 60 ° C. under an air stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. The solid concentration was about 32% (A13) (B).

Synthesis Example 4: Synthesis of organic-inorganic composite (A14) (B) within the scope of the present invention MEK-ST 111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, and aluminum acetylacetonate 0.025 g were added. After stirring until uniform, 0.99 g of pure water was added and stirred at room temperature for 3 hours. Thereafter, 10 g of stearyl methacrylate, 60 g of methyl methacrylate, 30 g of cyclomer M100 (manufactured by Daicel) and 200 g of MEK were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid concentration was about 32% (A14) (B).

Synthesis Example 5: Synthesis of organic-inorganic composite (A15) (B) outside the scope of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, and aluminum acetylacetonate 0.025 g were added. After stirring until uniform, 1.50 g of pure water was added and stirred at room temperature for 3 hours. This was mixed with 30 g of perfluorooctylethyl methacrylate, 60 g of methyl methacrylate, and 200 g of MEK, and then the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. The solid concentration was about 32% (A15) (B). The obtained organic polymer does not substantially have a group capable of being polymerized by irradiation with active energy rays.

Synthesis Example 6: Synthesis of organic polymer (A16) outside the range of the present invention 30 g of perfluorooctylethyl methacrylate, 70 g of methyl methacrylate, and 200 g of MEK were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. Organic polymer (A16) whose solid content concentration was about 33%. The obtained organic polymer has no group capable of being polymerized by irradiation with active energy rays.

Synthesis Example 7: Synthesis of organic polymer (A17) outside the scope of the present invention 10 g of α, ω-shaped mercaptopolydimethylsiloxane (X-22-167B manufactured by Shin-Etsu Chemical Co., Ltd.), 90 g of methyl methacrylate, and 200 g of MEK were added, and the internal temperature Was heated to about 60 ° C. under a nitrogen stream. Then, V65 was divided into 2 times, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid content was 33% (A17).
The obtained organic polymer has no group capable of being polymerized by irradiation with active energy rays.

Synthesis Example 8: Synthesis of organic-inorganic composite (A18) (B) outside the range of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, and aluminum acetylacetonate 0.025 g were added. After stirring until uniform, 1.00 g of pure water was added and stirred at room temperature for 3 hours. After mixing 70 g of methyl methacrylate, 20 g of cyclomer M100 (manufactured by Daicel) and 200 g of MEK, the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. The solid concentration was about 32%. Since the obtained organic polymer does not have a stain resistance imparting group, the contact angle of the coating film does not become 80 degrees or more.

Synthesis Example 9: Synthesis of organic-inorganic composite (A21) (B) within the scope of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, perfluorooctylethyltrimethoxysilane 2 g, After adding 0.025 g of aluminum acetylacetonate and stirring until uniform, 1.50 g of pure water was added and stirred at room temperature for 3 hours. After mixing 30 g of perfluorooctylethyl methacrylate, 50 g of methyl methacrylate, 10 g of cyclomer M100 (manufactured by Daicel) and 200 g of PGM, the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. The solid concentration was about 32%.
Next, a mixture of 37.2 g of acrylic acid / 10 g of PGM was added over about 20 minutes, and then the internal temperature was raised to 110 ° C. and maintained and stirred for 8 hours or more to complete the reaction between acrylic acid and epoxy groups. The content mixture was returned to room temperature. The solid content concentration was about 33%, and the desired product was obtained (A21) (B).

Synthesis Example 10: Synthesis of organic-inorganic composite (A22) (B) within the scope of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, and aluminum acetylacetonate 0.025 g were added. After stirring until uniform, 1.50 g of pure water was added and stirred at room temperature for 3 hours. This was mixed with 30 g of perfluorooctylethyl methacrylate, 50 g of methyl methacrylate, 10 g of hydroxymethyl methacrylate and 200 g of MEK, and then the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. The solid concentration was about 32%.
Subsequently, 18.3 g of an equimolar reaction product of hydroxyethyl acrylate and isophorone diisocyanate, 0.1 g of dibutyltin dilaurate and 0.1 g of p-methoxyphenol were added thereto, heated at room temperature for 2 hours, and then heated to 70 ° C. The temperature was maintained for 3 hours and then returned to room temperature. The solid concentration was about 37% (A22) (B).

Synthesis Example 11: Synthesis of organic-inorganic composite (A23) (B) within the scope of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, and aluminum acetylacetonate 0.025 g were added. After stirring until uniform, 1.50 g of pure water was added and stirred at room temperature for 3 hours. After mixing 28 g of perfluorooctylethyl methacrylate, 2 g of α, ω-dimercaptopolydimethylsiloxane (Shin-Etsu Chemical Co., Ltd., X-22-167B), 50 g of methyl methacrylate, 10 g of hydroxymethyl methacrylate, and 200 g of MEK, the internal temperature was changed to a nitrogen stream. The temperature was raised to about 60 ° C. below. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. The solid concentration was about 32%. Subsequently, 18.3 g of an equimolar reaction product of hydroxyethyl acrylate and isophorone diisocyanate, 0.1 g of dibutyltin dilaurate and 0.1 g of p-methoxyphenol were added thereto, heated at room temperature for 2 hours, and then heated to 70 ° C. The temperature was maintained for 3 hours and then returned to room temperature. The solid concentration was about 37% (A23) (B).

Synthesis Example 12: Synthesis of organic-inorganic composite (A24) (B) within the scope of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, and aluminum acetylacetonate 0.025 g were added. After stirring until uniform, 0.99 g of pure water was added and stirred at room temperature for 3 hours. Thereafter, 10 g of stearyl methacrylate, 60 g of methyl methacrylate, 30 g of cyclomer M100 (manufactured by Daicel) and 200 g of PGM were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid concentration was about 30%.
Next, a mixture of 37.2 g of acrylic acid / 10 g of PGM was added over about 20 minutes, and then the internal temperature was raised to 110 ° C. and maintained and stirred for 8 hours or more to complete the reaction between acrylic acid and epoxy groups. . The content mixture was returned to room temperature. The solid concentration was about 33%, and the intended (A24) (B) was obtained.

Synthesis Example 13: Synthesis of organic-inorganic composite (A25) (B) outside the scope of the present invention MEK-ST111 g, mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) 3 g, and aluminum acetylacetonate 0.025 g were added. After stirring until uniform, 1.50 g of pure water was added and stirred at room temperature for 3 hours. After mixing 30 g of perfluorooctylethyl methacrylate, 60 g of methyl methacrylate and 200 g of MEK, the internal temperature is raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated, and then the content mixture was returned to room temperature. This organic-inorganic composite has no group capable of being polymerized by irradiation with active energy rays.

Synthesis Example 14: Synthesis of silane coupling agent having polyfunctional acrylic group by reaction of OH-containing polyfunctional acrylate and NCO-containing silane coupling agent Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Nippon Kayaku, After stirring and mixing 1 kg of Kayarad DPHA), 50 g of γ-triethoxysilylpropyl isocyanate (Shin-Etsu Silicone, KBE9007), 0.2 g of dibutyltin dilaurate and 0.5 g of hydroquinone monomethyl ether, the temperature was raised to 90 ° C. in an air stream, and the temperature For 1 hour. It was confirmed by IR that the absorption corresponding to the NCO group had completely disappeared, and then returned to room temperature, and the product was taken out (silane coupling agent 1, hereinafter referred to as SC1). The reaction was quantitative.

Synthesis Example 15: A (meth) acryloyl group is bonded to the surface of an inorganic oxide fine particle through a -O-Si-R- bond by a reaction between colloidal silica and a silane coupling agent having a polyfunctional acrylic group. Of the organic / inorganic composite (A ′) (B1) 400 g of the MEK-ST (30% MEK solution), 400 g of the SC1, 400 g of hydroquinone monomethyl ether, and 4 g of acetylacetone aluminum were mixed thoroughly and purified water. 8 g was added, and stirring was continued for 3 hours or more at room temperature. Thereafter, the temperature is raised to 50 to 70 ° C. in an air atmosphere, and stirring is continued for 2 hours or more at that temperature, and a silane coupling agent is reacted with the surface of the silica sol to form a protective colloid. ') (B1) was obtained.

Synthesis Example 16: A (meth) acryloyl group is bonded to the surface of an inorganic oxide fine particle through a -O-Si-R- bond by a reaction between colloidal silica, a silane-terminated polymer having an acrylic group, and colloidal silica. Synthesis of Organic-Inorganic Composite (A ′) (B2) After mixing 95 g of glycidyl methacrylate, 3 g of mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) and 200 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc) The internal temperature was raised to about 60 ° C. in a nitrogen stream. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 100 ° C., and V65 was completely deactivated. Then, 200 g of PGMAc and 1.5 g of triphenylphosphine were added, and stirring was continued in an air atmosphere until uniform. Thereafter, a mixture of 49 g of acrylic acid / 10 g of PGMAc was added over about 20 minutes, and then the internal temperature was raised to 110 ° C. and maintained and stirred for 8 hours or more to complete the reaction between acrylic acid and epoxy groups. After returning the content mixture to room temperature, 163 g of MEK-ST and 0.04 g of aluminum acetylacetonate were added, and after stirring until uniform, 0.99 g of pure water was added, and the mixture was stirred at room temperature for 3 hours at 50 ° C to 70 ° C. The reaction was performed at 4 ° C. for about 4 hours. Thereafter, the internal temperature was returned to room temperature. The solid content concentration was about 30%, and the intended organic-inorganic composite (A ′) (B2) was obtained.

Synthesis Example 17: A (meth) acryloyl group is bonded to the surface of an inorganic oxide fine particle through a —O—Si—R— bond by a reaction between colloidal silica, a silane-terminated polymer having an acrylic group, and colloidal silica. Synthesis of Organic / Inorganic Composite (A ′) (B3) 95 g of glycidyl methacrylate, 3 g of mercaptopropyltrimethoxysilane (KBE 803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 200 g of PGMAc were mixed, and the internal temperature was changed to about 60 with nitrogen flow. The temperature was raised to ° C. Thereafter, V65 was divided into two portions and 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 100 ° C., and V65 was completely deactivated. Then, 200 g of PGMAc and 1.5 g of triphenylphosphine were added, and stirring was continued in an air atmosphere until uniform. Thereafter, a mixture of 39 g of acrylic acid / 10 g of PGMAc was added over about 20 minutes, and then the internal temperature was raised to 110 ° C. and maintained and stirred for 8 hours or more to complete the reaction between acrylic acid and epoxy groups. After returning the content mixture to room temperature, 163 g of MEK-ST and 0.04 g of aluminum acetylacetonate were added. After stirring until uniform, 0.99 g of pure water was added, and at room temperature for 3 hours at 50 to 70 ° C. The reaction was performed for about 4 hours. Thereafter, the internal temperature was returned to room temperature. The solid content concentration was about 28%, and the target organic-inorganic composite (A ′) (B3) was obtained.

Example 1
(A11) (B) 1 part by weight of Irgacure 250 (manufactured by Ciba Specialty Chemicals, iodonium salt-based photocationic polymerization initiator), 2 parts of Irgacure 184, (A ′) ) After adjusting the solid content of (B1) to 90 parts and PGM to a solid content of 30%, an acrylic film having a thickness of 125 μm (manufactured by Mitsubishi Rayon, haze value 0.2%) has a thickness after drying of 1 μm. It was applied and then dried at 80 ° C. to remove the solvent and form a dry film. This was cured using a high-pressure mercury lamp having an output density of 120 W / cm, and the coating film was evaluated for transparency, warpage, pencil hardness, adhesion, and abrasion resistance. The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Examples 2-16
In the first embodiment, (A11) (B) is changed to (A12) (B), (A13) (B), (A14) (B), and (A ′) (B1) is changed to (A ′) (B2). (A ') (B3) or a mixture thereof / or coating film thickness / or base material / or concentration was changed, and the coating film was prepared in the same manner. The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Comparative Examples 1-8
In Example 1 above, the composition was as shown in Table 1, and the others were the same as in Example 1 to prepare a coating film. The evaluation results are shown in Table 2. These were inferior in durability and hardness in comparison with those included in the scope of the present invention.

In the above table, (A) (B) complex, (A ′) (B) complex component (C) to component (D) may indicate these alternative substances in the comparative examples.
In the above table, I250 means Irgacure 250, which is a polymerization initiator by irradiation with a photocationic (iodonium salt) active energy ray. I184 means Irgacure 184 and is a radical photopolymerization initiator. I907 means and is a radical photopolymerization initiator. OXE01 means Irgacure OXE01 and is a radical photopolymerization initiator. These are all manufactured by Ciba Specialty Chemicals.
PET represents a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film, T600EU07, thickness 100 μm (haze value 1.1%)). PC represents a polycarbonate film (manufactured by GE, Lexan film, thickness 500 μm (haze value 0.2%)) (hereinafter the same).

Example 17
(A11) (B) (solid content 32%) 10 parts by weight of solid content Irgacure 2501 parts, Irgacure 184 2 parts, (B1) solid content 90 parts, Sanol LS765 (Sankyo) 3 parts, Tinuvin 4 parts of P (manufactured by Ciba Specialty Chemicals), adjusted to 30% solid content with PGM, and then dried to 125 μm thick acrylic film (Mitsubishi Rayon, haze value 0.2%) so that the thickness after drying becomes 1 μm And then dried at 80 ° C. to remove the solvent and form a dry film. This was cured using a high-pressure mercury lamp with an output density of 120 W / cm, and the coating film was evaluated for transparency, pencil hardness, contact angle, and adhesion. The composition is shown in Table 1, and the evaluation results are shown in Table 2.
Furthermore, when antifouling property evaluation was conducted by a method in accordance with Type I of the antifouling material promotion test for civil engineering (change the solution to a test solution of 95% water and 5% carbon black),-△ * was -0.0. Excellent anti-contamination property, and-△ * maintains an excellent anti-contamination property of -0.1 even after 500 hours test with Q-UV, and excellent anti-contamination property It could be confirmed.

Example 21
(A21) (B) 2 parts of Irgacure OXE01 (manufactured by Ciba Specialty Chemicals), 2 parts of Irgacure 907, 90 parts of solid content of (B1), 10 parts by weight of PGM, based on 10 parts by weight of solid content (solid content 32%) After adjusting to 30% per minute, it was applied to a 100 μm thick acrylic film (Mitsubishi Chemical Polyester Film, haze value 1.1%) so that the thickness after drying was 5 μm, and then dried at 80 ° C., The solvent was removed to form a dry film. This was cured using a high-pressure mercury lamp with an output density of 120 W / cm, and the coating film was evaluated for transparency, warpage, pencil hardness, adhesion, and abrasion resistance. The composition is shown in Table 3, and the evaluation results are shown in Table 4.

Examples 22 to 36, Comparative Examples 21 to 26
In Example 21, (A21) and (B) are sequentially changed to (A22), (B), (A23), (B), (A24), and (B), and (A ′) and (B1) are changed to (A ′) and (B2). ), (A ′), (B3), or a mixture thereof / or the thickness of the coating film / or the substrate was changed, and the coating film was prepared in the same manner. Detailed composition is shown in Table 3, and evaluation results are shown in Table 4.

Comparative Examples 21-26
A coating film was prepared in the same manner as in Example 21 except that the formulation in Example 21 was as shown in Table 3. The evaluation results are shown in Table 4. These were inferior in durability and hardness in comparison with those included in the scope of the present invention.

Comparative Example 27
(D) The coating film was created like Example 23 except not containing a component. Detailed formulations are shown in Table 3, and evaluation results are shown in Table 4. These were significantly inferior in hardness or the like as compared with those included in the scope of the present invention.

Example 37
(A21) (B) 1 part by weight of Irgacure 250 (manufactured by Ciba Specialty Chemicals, iodonium salt-based photocationic polymerization initiator), 2 parts of Irgacure 184, (A ′) ) After adjusting the solid content of (B1) to 90 parts, Sanol LS765 (Sankyo) to 3 parts, Tinuvin P (Ciba Specialty Chemicals) to 4 parts, and PGM to 30% solid content, a 125 μm thick acrylic film (Mitsubishi Rayon) Manufactured, having a haze value of 0.2%), the thickness after drying was 1 μm, and then dried at 80 ° C. to remove the solvent and form a dry film. This was cured using a high-pressure mercury lamp with an output density of 120 W / cm, and the coating film was evaluated for transparency, pencil hardness, contact angle, and adhesion. Detailed formulations are shown in Table 3, and evaluation results are shown in Table 4.
About this, when the antifouling property evaluation was carried out by the method based on the type I antifouling material promotion test type I in the same manner as in Example 17, -ΔL * was -0.0 and excellent in antifouling property. Even after the 500-hour test with Q-UV, -ΔL * was maintained at -0.1 and excellent antifouling property, and it was confirmed that the antifouling property was also excellent.

Further, each of the samples of Examples 1 to 17, Comparative Examples 1 to 8, Examples 21 to 37, and Comparative Examples 21 to 27 was evaluated for durability of contamination resistance (fingerprint resistance). Specifically, the wiping feeling and adhesion when the fingerprint wiping property (1-1), fingerprint wiping property (1-50), fingerprint wiping property (2), and fingerprint wiping property (2) were performed were evaluated.
The results are shown in Tables 5 and 6.

Example 18 and Example 38
The F / C ratio of the coating film of Example 1 or Example 21 was measured with ESCA (Shimadzu Corporation ESCA1000). The average composition of the coating film is F / C = 0.071, whereas the composition at 3 nm from the coating film surface is F / C = 0.263, and the fluorine atoms are concentrated 3.7 times on the surface. It has been confirmed that.
From this result, even if the amount of the stain resistance imparting group in the stain resistance imparting agent is, for example, 1% by weight, the stain resistance imparting group is efficiently concentrated on the surface of the coating film, resulting in high stain resistance. It was recognized that it was possible to realize.

Claims (20)

Inorganic oxide fine particles (B) containing colloidal silica as a main component, and —O—Si—R— bond (wherein R represents a linear or branched alkylene group having 2 to 10 carbon atoms). An organic-inorganic composite having an organic polymer (A) bonded via the organic polymer (A), wherein the organic polymer (A) is an active energy ray independent of the stain resistance imparting group and the stain resistance imparting group. A film having a thickness of 5 μm formed by coating the organic-inorganic composite on a PET substrate having a thickness of 100 μm and polymerizing by irradiation with active energy rays. Is a stain resistance imparting agent having a pencil hardness of F or more and a water contact angle of 80 degrees or more. The antifouling agent according to claim 1, wherein the antifouling group is at least one group selected from the group consisting of an organo (poly) siloxane group, an organic fluorine compound group, and a linear alkyl group having 12 or more carbon atoms. . The antifouling agent according to claim 1 or 2, wherein the group capable of being polymerized by irradiation with active energy rays is a group capable of photocationic polymerization. The antifouling agent according to claim 3, wherein the photocationically polymerizable group is an epoxy group and / or an oxetane group. The antifouling agent according to claim 1 or 2, wherein the group capable of being polymerized by irradiation with active energy rays is a radical capable of radical photopolymerization. The antifouling agent according to claim 5, wherein the radically polymerizable group is a (meth) acryloyl group. The stain resistance imparting agent according to any one of claims 1 to 6, comprising a cationic polymerizable photoinitiator (C). The stain resistance imparting agent according to any one of claims 1 to 7, comprising a radical polymerizable photoinitiator (D). Further, radical polymerizable organic (meth) acrylate compound and / or radical polymerizable organic (meth) acrylamide compound (E), polymer (F) having radical polymerizable group, organic epoxy compound (G) and organic oxetane compound The antifouling agent according to any one of claims 1 to 8, comprising at least one member selected from the group consisting of (H). Furthermore, it comprises an ultraviolet absorber (I), a hindered amine light stabilizer (J), an antistatic agent (K), a slipperiness imparting agent (L), an antifogging imparting agent (M), and a peelability imparting agent (N). The antifouling agent according to any one of claims 1 to 9, comprising at least one member of the group. Furthermore, inorganic oxide fine particles (B) mainly composed of colloidal silica, and —O—Si—R— bonds (where R is a linear or branched alkylene group having 2 to 10 carbon atoms) are added to the inorganic oxide fine particles. The stain resistance imparting agent according to claim 1, comprising an organic-inorganic composite having an organic component (A ′) having a (meth) acryloyl group bonded via Hardened | cured material formed by irradiating an active energy ray and polymerizing the contamination | pollution resistance imparting agent in any one of Claims 1-11. An article having, on the surface, a film obtained by polymerizing the stain resistance-imparting agent according to any one of claims 1 to 11 by irradiation with active energy rays. When the antifouling agent is applied onto a PET substrate having a thickness of 100 μm and polymerized by irradiation with active energy rays, a film having a thickness of 5 μm is formed. The stain resistance imparting agent according to any one of claims 1 to 11, wherein the content of the stain resistance imparting group is at least three times the average content of the stain resistance imparting group of the entire film. When the antifouling agent is applied onto a PET substrate having a thickness of 100 μm and polymerized by irradiation with active energy rays, the film is usually cured under an oxygen concentration atmosphere. The antifouling agent according to any one of claims 1 to 11 and 14, wherein the wear resistance is 25.0 or less and the amount of warpage is 1 mm or less. When the antifouling agent is applied onto a 100 μm thick PET substrate and polymerized by irradiation with active energy rays, the film has a haze value of 1.5% or less. The antifouling agent according to any one of claims 1 to 11, 14, and 15. Inorganic oxide fine particles (B) containing colloidal silica as a main component, and —O—Si—R— bond (wherein R represents a linear or branched alkylene group having 2 to 10 carbon atoms). An organic-inorganic composite having an organic polymer (A) bonded via the organic polymer (A), wherein the organic polymer (A) is an active energy ray independent of the stain resistance imparting group and the stain resistance imparting group. And a group that can be polymerized by irradiation. The organic polymer (A) includes a contamination-resistant group-containing radical polymerizable monomer (A-1) in an amount of 1 to 40% by weight and a group capable of being polymerized by irradiation with active energy rays in the main chain and / or side chain. 1 to 60% by weight of the radically polymerizable monomer (A-2) that can be introduced, and the radically polymerizable monomer (A-3) that can be polymerized with the monomer (A-1) and the monomer (A-2) 0 to 80 The composition according to claim 17, wherein the composition is polymerized with weight%. Furthermore, inorganic oxide fine particles (B) mainly composed of colloidal silica, and —O—Si—R— bonds (where R is a linear or branched alkylene group having 2 to 10 carbon atoms) are added to the inorganic oxide fine particles. The composition according to claim 17 or 18, comprising an organic-inorganic composite having an organic component (A ') having a (meth) acryloyl group bonded thereto. Inorganic oxide fine particles (B) containing colloidal silica as a main component, and —O—Si—R— bond (wherein R represents a linear or branched alkylene group having 2 to 10 carbon atoms). And an organic-inorganic composite having a stain resistance imparting group and a group capable of being polymerized by irradiation with an active energy ray independently of the stain resistance imparting group.