JPWO2014115730A1 - Surface-treated silicon-containing resin composition film, coating film or molded body, and surface treatment method thereof - Google Patents

Abstract

The present invention relates to a structural unit A derived from fluorosilsesquioxane having one addition-polymerizable functional group in the molecule, and a silyl having no polymerizable functional group in the molecule and does not contain fluorosilsesquioxane. The present invention relates to a cured product having a functional surface obtained by surface-treating a resin composition comprising at least one selected from structural units B derived from sesquioxane and a polymerizable resin C.

Description

  The present invention relates to a resin composition useful as a coating material, an optical material obtained by molding, an electrical insulating material, and the like. Furthermore, this invention relates to the molded object by which the surface containing the resin composition containing a fluoropolymer was modified | denatured.

  In recent years, light-emitting devices such as light-emitting diodes (LEDs) that have been put to practical use in various display boards, light sources for image reading, traffic signals, large display units, and backlights for mobile phones are hardened with aromatic epoxy resins. In general, the resin is sealed with a resin using an alicyclic acid anhydride. However, it is known that in this resin system, an acid anhydride is easily discolored by an acid, and a long time is required for curing. Further, when the cured sealing resin is left outdoors or exposed to a light source that generates ultraviolet rays, there is a problem that the sealing resin turns yellow.

  In order to eliminate such problems, attempts have been made to use a cyclic aliphatic epoxy resin or an acrylic resin to seal a resin such as an LED with a cationic polymerization initiator (see Patent Documents 1 and 2). . However, the cation-polymerized cured resin is very brittle, so that it is liable to be cracked by a thermal cycle, and the sealing resin after curing is significantly colored compared to the conventional aromatic epoxy resin-acid anhydride curing system. It has a serious drawback. Therefore, this curable resin is not suitable for applications requiring colorless transparency, particularly for LED sealing applications requiring heat resistance and transparency.

  Then, generation | occurrence | production of the crack by a cold-heat cycle is improved, and the resin composition for LED sealing materials excellent in light resistance is disclosed by patent document 3. FIG. Although the resin composition shown here uses a hydrogenated epoxy resin or an alicyclic epoxy resin as a matrix component, it still has a large change over time after curing, and further quality stability has been desired.

  On the other hand, Patent Document 4 describes an embedded resin composition for filling a gap between an electronic component of a wiring board and a board using an aliphatic cyclic epoxy resin or oxetane resin as a viscosity reducing agent. However, the resin composition contains a large amount of an inorganic filler and cannot be applied to a field requiring transparency.

  Patent Document 5 discloses a resin composition that is soluble in an alkaline aqueous solution using a modified oxetane resin as an active energy ray-curable resin, and the one shown here should be an alkali-soluble resin. Moreover, since the modified oxetane resin and the polyfunctional oxetane resin have an unsaturated bond, discoloration due to heat history is inevitable.

Japanese Unexamined Patent Publication No. 61-112334 Japanese Laid-Open Patent Publication No. 02-289611 Japanese Unexamined Patent Publication No. 2003-277473 Japanese Unexamined Patent Publication No. 2004-27186 International Publication No. 2001/072857 Japanese Unexamined Patent Publication No. 2006-070049 International Publication No. 2004/081084 Japanese Unexamined Patent Publication No. 2004-331647 International Publication No. 2003/24870 International Publication No. 2004/24741 International Publication No. 2008/72765 Japanese Unexamined Patent Publication No. 2009-114409 Japanese Unexamined Patent Publication No. 2012-46752

  The present invention is to expose a cured film with ultraviolet light or an electron beam to form a crosslinked polymer of a crosslinked group in a copolymer, to obtain a solvent-insoluble ultrathin film, and various optical elements An object of the present invention is to provide a curable resin composition that can be subjected to a protective film such as a magnetic head, surface modification, and surface treatment to various materials.

  As a result of intensive studies, the present inventors have found that the structural unit A derived from fluorosilsesquioxane having one addition-polymerizable functional group in the molecule and a plurality of units containing no fluorosilsesquioxane and in the molecule By surface-treating a resin composition comprising at least one selected from the structural unit B derived from silsesquioxane having a polymerizable functional group and a polymerizable resin C, the coating strength is improved, and superhydrophilicity is achieved in a short time. The present inventors have found that a functional film having a functional surface can be obtained.

That is, the present invention is as follows.
(1) Structural unit A derived from fluorosilsesquioxane having one addition-polymerizable functional group in the molecule, and silsesquioxane not containing fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule A cured product having a functional surface obtained by surface-treating a monomer composition that provides at least one structural unit selected from structural units B derived from oxane and a polymerizable resin C.
(2) The cured product according to (1) above, wherein the fluorosilsesquioxane having one addition polymerizable functional group is represented by the following formula (1).

In formula (1), R _f ^{1 to} R _f ⁷ are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is fluorine or trifluoro A fluoroaryl having 6 to 20 carbon atoms replaced by methyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl is replaced by fluorine or trifluoromethyl, and A ¹ is An addition polymerizable functional group is shown.

(3) R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6- The cured product according to (2) above, which exhibits nonafluorohexyl or tridecafluoro-1,1,2,2-tetrahydrooctyl.
(4) The cured product according to (2) or (3) above, wherein A ¹ in the formula (1) is a radical polymerizable functional group.
(5) The cured product according to (4) above, wherein A ¹ in the formula (1) contains (meth) acryl or styryl.
(6) The cured product according to (5), wherein A ¹ in the formula (1) is represented by the following formula (3) or (5).

In the formula (3), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ⁶ is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, and in the formula (5), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms.
(7) In the formula (3), Y ¹ represents alkylene having 2 to 6 carbon atoms, R ⁶ represents hydrogen or methyl, and in the formula (5), Y ² represents a single bond or 1 or 2 carbon atoms. Hardened | cured material as described in said (6) which shows alkylene.

(8) At least one silsesquioxane in which the structural unit B derived from silsesquioxane not containing the fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule is represented by the following structure: Hardened | cured material as described in said (1) containing a derivative | guide_body.

In the formula (A-1) to the formula (A-3), each R is independently hydrogen, a non-adjacent —CH ₂ — may be replaced with —O— or cycloalkylene, and the carbon number is 1 to 45 Alkyl, cycloalkyl having 4 to 8 carbon atoms, or substituted or unsubstituted aryl. In the substituted benzene ring, any hydrogen may be replaced with alkyl having 1 to 10 carbon atoms or halogen. R ¹ is a group independently selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl. At least one X is a group having hydrogen or a polymerizable functional group, and the remaining X is a group defined in the same manner as R ¹ .
(9) Hardened | cured material as described in said (8) whose R is a phenyl group or a cyclohexyl group in said Formula (A-1)-Formula (A-3).

(10) The cured product according to (8), wherein X is a group represented by any one of formula (2), formula (3), formula (4), and formula (5).

(11) A silsesquioxane derivative in which the structural unit B derived from silsesquioxane not containing the fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule is represented by the following formula (1-1) The cured product according to (8) above.

(12) Any one of the above (1) to (11), wherein the polymerizable resin C is one or more kinds of resins selected from thermoplastic resins, thermosetting resins and / or active energy ray curable resins. Hardened | cured material as described in.

(13) The polymerizable resin C contains (meth) acrylate resin, polyurethane resin, biodegradable resin, polyvinyl alcohol resin, urethane acrylate resin, polyolefin resin, epoxy resin not containing silicon in the molecule, and silicon in the molecule. Hardened | cured material of any one of said (1)-(12) which is at least 1 or more types of resin chosen from the oxetane resin which does not contain.
(14) The cured product according to (1), wherein the surface treatment is an ozone treatment and / or an ultraviolet irradiation treatment.
(15) The cured product according to (1), wherein the functional surface provided by the surface treatment is a superhydrophilic surface.
(16) The cured product according to (1), wherein the functional surface provided by the surface treatment is a gas barrier layer.

(17) The cured product according to (1), wherein the functional surface provided by the surface treatment is a hard coat layer.
(18) The cured product according to (1), wherein the functional surface provided by the surface treatment is a heat-resistant surface.
(19) Structural unit A derived from fluorosilsesquioxane having one addition-polymerizable functional group in the molecule, and silsesquioxane not containing fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule A film, a coating film, or a molded article prepared from a resin composition comprising a monomer compound that provides at least one structural unit selected from structural units B derived from oxane and a polymerizable resin C.
(20) Structural unit A derived from fluorosilsesquioxane having one addition-polymerizable functional group in the molecule, and silsesquidex not containing fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule A resin composition comprising a monomer compound giving at least one structural unit selected from structural units B derived from oxane and a polymerizable resin C, wherein the resin composition is cured and surface-treated (film) A resin composition having a surface contact angle of less than 10 °.

  The resin composition of the present invention includes a structural unit A derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule and a plurality of polymerizable functional groups in the molecule. At least one selected from a structural unit B derived from a silsesquioxane having a group and a polymerizable resin C, and the resin composition is cleaved by a bond between an organic group and a silicon atom by deep ultraviolet rays or ozone. Since a siloxane bond can be formed by bonding an oxygen atom to a portion, the coating strength is improved by surface treatment, and a functional film having a superhydrophilic surface can be obtained in a short time. The cured product obtained by surface-treating the resin composition of the present invention is excellent in hydrophilicity, thermal stability, physical strength, uniformity and the like and can be suitably used as an electronic material.

  The cured product of the present invention includes a structural unit A derived from a fluorosilsesquioxane having an addition polymerizable functional group, and a silsesquioxy which does not contain fluorosilsesquioxane and has a plurality of polymerizable functional groups in the molecule. It is a cured product having a functional surface obtained by surface-treating a resin composition comprising at least one selected from the structural unit B derived from Sun and a polymerizable resin C.

  In the present invention, the addition polymerizable functional group means a functional group capable of addition polymerization, and “derived” means a polymerized residue when each monomer constitutes the resin composition of the present invention. The molar fraction (%) of the structural unit A in the resin composition is represented by a, the molar fraction (%) of the structural unit B in the resin composition is represented by b, and the polymerizable resin C in the resin composition The molar fraction (%) is represented by c and satisfies 0 <a <100, 0 <b <100, 0 <c <100, and a + b + c = 100, respectively.

  In the present invention, “polymerizable resin C” is a general term for a high molecular weight polymerizable resin, a polymerizable oligomer having a weight average molecular weight of several hundred to several thousand, and a polymerizable monomer.

  The resin composition of the present invention does not contain, for example, a fluorosilsesquioxane having one addition polymerizable functional group in the molecule and a fluorosilsesquioxane having an addition polymerizable functional group, and a plurality of polymerizations in the molecule. It can be obtained by copolymerizing silsesquioxane having a functional functional group and an addition polymerizable monomer (polymerizable resin C).

  First, fluorosilsesquioxane having one addition polymerizable functional group in the molecule will be described.

Fluorosilsesquioxane has a silsesquioxane skeleton in its molecular structure. Silsesquioxane is a general term for polysiloxanes represented by [(R—SiO _1.5 ) n] (R is an optional substituent). The structure of this silsesquioxane is generally classified into a random structure, a ladder structure, and a cage structure according to the Si—O—Si skeleton. Furthermore, the cage structure is classified into T8, T10, T12 type and the like. Among them, the fluorosilsesquioxane used in the present invention is characterized by having at least one addition polymerizable functional group. That is, one of R in silsesquioxane [(R—SiO _1.5 ) n] is an addition polymerizable functional group.

  Examples of the addition polymerizable functional group include a group having a terminal olefin type or an internal olefin type radical polymerizable functional group; a group having a cationic polymerizable functional group such as vinyl ether, propenyl ether and epoxy group; vinyl carboxyl and And a group having an anion polymerizable functional group such as cyanoacryloyl. A group having a cationic polymerizable functional group such as an epoxy group or a radical polymerizable functional group is preferable.

  The radical polymerizable functional group is not particularly limited as long as it is a radical polymerizable group. For example, methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N- Examples include vinyl amide, maleic acid ester, fumaric acid ester and N-substituted maleimide. Among them, a group containing (meth) acryl or styryl is preferable. Here, (meth) acryl is a general term for acrylic and methacrylic and means acrylic and / or methacrylic. The same shall apply hereinafter.

  Examples of the radical polymerizable functional group having the (meth) acryl include a group represented by the following formula (3).

In Formula (3), Y ¹ represents alkylene having 2 to 10 carbon atoms, preferably represents alkylene having 2 to 6 carbon atoms, and more preferably represents alkylene (propylene) having 3 carbon atoms. R ⁶ represents hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, preferably hydrogen or alkyl having 1 to 3 carbon atoms, more preferably hydrogen or methyl. Here, the alkyl having 1 to 5 carbon atoms may be either linear or branched. Moreover, the group shown by the following formula | equation (5) is contained in the example of the radically polymerizable functional group which has said styryl. In Formula (5), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms, preferably a single bond or alkylene having 1 to 6 carbon atoms, more preferably a single bond or alkylene having 1 or 2 carbon atoms. And particularly preferably a single bond or alkylene (ethylene) having 2 carbon atoms. Vinyl is bonded to any carbon of the benzene ring, preferably bonded to carbon in the para position with respect to Y ² .

Said fluorosilsesquioxane has at least one fluoroalkyl, fluoroarylalkyl or fluoroaryl. That is, at least one R of silsesquioxane (R—SiO _1.5 ) n, preferably R other than the above addition polymerizable functional group, is fluoroalkyl, fluoroarylalkyl and / or fluoroaryl.

The fluoroalkyl may be linear or branched. This fluoroalkyl has 1 to 20 carbon atoms, preferably 3 to 14 carbon atoms. Furthermore, any methylene of the fluoroalkyl may be replaced with oxygen. Here, methylene includes —CH ₂ —, —CFH— or —CF ₂ —. That is, “any methylene may be replaced with oxygen” means that —CH ₂ —, —CFH—, or —CF ₂ — may be replaced with —O—. However, in fluoroalkyl, two oxygens are not bonded (—O—O—). That is, the fluoroalkyl may have an ether bond. Also, in the preferred fluoroalkyl, the methylene adjacent to Si is not replaced with oxygen, and the end opposite to Si is CF ₃ . Furthermore, it is preferable that —CF ₂ — be replaced with oxygen rather than —CH ₂ — or —CFH— to be replaced with oxygen. Preferred specific examples of such fluoroalkyl include 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrododecyl, henicosafluoro-1,1,2,2-tetrahydro Dodecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl and the like are included. Among these, perfluoroalkyl ethyl are preferred examples, -CH 2 _-CH 2 _- to the fluoroalkyl group may be bonded groups via, -CH 2 _- fluoroalkyl group is linked via a It may be a group.

  The fluoroarylalkyl is an alkyl containing an aryl containing fluorine, and preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. The fluorine contained is preferably one in which any one or more hydrogens in aryl are replaced with fluorine or trifluoromethyl. Aryl moieties include, for example, phenyl, naphthyl and heteroaryl. Alkyl moieties include, for example, methyl, ethyl and propyl.

  The fluoroaryl is one in which any one or two or more hydrogens in the aryl are replaced by fluorine or trifluoromethyl, and preferably has 6 to 20 carbon atoms, more preferably 6. Such aryl includes, for example, phenyl, naphthyl and heteroaryl. Specific examples include fluorophenyl such as pentafluorophenyl and trifluoromethylphenyl.

  Of the fluoroalkyl, fluoroarylalkyl or fluoroaryl contained in fluorosilsesquioxane, a preferred group is fluoroalkyl, more preferably perfluoroalkylethyl, and still more preferably 3,3,3-trimethyl. Fluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl or tridecafluoro-1,1,2,2-tetrahydrooctyl.

  As mentioned above, preferred fluorosilsesquioxanes have a T8 type structure, have one addition polymerizable functional group, and one or more fluoroalkyl, fluoroarylalkyl and / or fluoroaryl. And is represented by the following structural formula (1).

In the formula (1), A ¹ is an addition polymerizable functional group, preferably the aforementioned radical polymerizable functional group, and R _f ^{1 to} R _f ⁷ are each independently the aforementioned fluoroalkyl, fluoro Arylalkyl or fluoroaryl is preferred. R _f ^{1 to} R _f ⁷ may be different groups or all may be the same group.

R _f ^{1 to} R _f ⁷ in formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4, 5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, hepadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1 , 1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α, α-trifluoromethylphenyl is preferable, and R _f ^{1 to} R _f ⁷ are each independently 3,3,3-trifluoropropyl, 3,3,4 , 4,5,5,6,6,6-nonafluorohexyl or tridecafluoro-1,1,2,2-tetrahydrooctyl.

  Specific examples of the compound include compound (a-1) described in [Production Example 1] of International Publication No. 2008/072765.

  Next, the structural unit B derived from silsesquioxane which does not contain fluorosilsesquioxane and has a plurality of polymerizable functional groups in the molecule will be described.

  The structural unit B of the resin composition of the present invention is at least one compound selected from silsesquioxane derivatives represented by formulas (A-1) to (A-3).

In the formula (A-1) to the formula (A-3), each R is independently hydrogen, a non-adjacent —CH ₂ — may be replaced with —O— or cycloalkylene, and the carbon number is 1 to 45 Alkyl, cycloalkyl having 4 to 8 carbon atoms, or substituted or unsubstituted aryl. In the substituted benzene ring, any hydrogen may be replaced with alkyl having 1 to 10 carbon atoms or halogen.

  More preferred R is cyclopentyl, cyclohexyl, or phenyl where any hydrogen may be replaced by chlorine, fluorine, methyl, methoxy, or trifluoromethyl, even more preferred R is cyclohexyl or phenyl, and most preferred R Is phenyl.

R ¹ is a group independently selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl. Examples of alkyl having 1 to 4 carbon atoms are methyl, ethyl, propyl, 2-methylethyl, butyl and t-butyl. Preferred examples of R ¹ are methyl and phenyl. R ¹ is preferably the same group.

At least two X are hydrogen or a group having a polymerizable functional group, and the remaining X is a group defined in the same manner as R ¹ . When X is a polymerizable functional group, examples include a substituent having any one of oxiranyl, oxiranylene, 3,4-epoxycyclohexyl, oxetanyl, oxetanylene, vinyl, allyl, or styryl. In the present invention, it is preferable to have one of oxiranyl, oxiranylene, 3,4-epoxycyclohexyl, oxetanyl and oxetanylene, and the residues of each substituent are shown below.

  Next, specific compounds belonging to the structural unit B are exemplified.

<Compound Example 1>
Compound Example 1 is described as Compound (1-1) in [Synthesis Example 1] in the examples of Japanese Patent Application Laid-Open No. 2009-167390, and is represented by the following formula.

<Compound Example 2>
Compound Example 2 is an example described in Japanese Patent Application Laid-Open No. 2007-326988, and is described as Compound (1-1) in [Synthesis Example 1] and represented by the following formula.

<Compound Example 3>
Compound Example 3 is described as Compound (b-1-1) in Example 1 of Japanese Patent Application Laid-Open No. 2010-254814 and is represented by the following formula.

  Next, the polymerizable resin C will be described.

  The fluorosilsesquioxane derivative of the structural unit A or the silsesquioxane derivative of the structural unit B can be used in combination with the polymerizable resin C. In the present invention, as described above, “polymerizable resin C” is a general term for a high molecular weight polymerizable resin, a polymerizable oligomer having a weight average molecular weight of several hundred to several thousand, and a polymerizable monomer. .

  In order to form a film on the substrate surface with the resin composition of the present invention, at least one selected from the fluorosilsesquioxane derivative of the structural unit A and the silsesquioxane derivative of the structural unit B has a crosslinking component. When the polymerizable resin C is blended and used, characteristics such as heat resistance, light resistance, scratch resistance, abrasion resistance, surface / interface characteristics, and compatibility of the cured film can be improved.

  Specifically, for example, a solution containing a silsesquioxane derivative having a polymerizable group, a polymerizable polyfunctional compound, and, if necessary, a polymerization initiator (curing reaction) is applied to a substrate, and a coating film is applied. By drying and curing, a film (composite film) made of the composite resin can be formed on the substrate.

  The polymerizable resin C may be either a thermoplastic resin or a thermosetting resin, and may be a plurality of types of compounds.

  Examples of the polymerizable resin C include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultrahigh molecular weight polyethylene, poly-4. -Methylpentene, syndiotactic polystyrene, polyamide (for example, nylon 6: DuPont brand name, nylon 6,6: DuPont brand name, nylon 6,10: DuPont brand name, nylon 6, T: DuPont brand name , Nylon MXD6: DuPont brand name, etc.), polyester (for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate), polyacetal, polycarbonate, polyphe Ren oxide, fluorine resin (eg, polytetrafluoroethylene, polyvinylidene fluoride), polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate [eg, U polymer: trade name of Unitika Ltd., Vectra: polyplastic Product name], polyimide [for example, Kapton: Toray Co., Ltd. trade name, AURUM: Mitsui Chemicals Co., Ltd. trade name], polyetherimide, polyamideimide, phenol resin, alkyd resin, melamine resin, epoxy resin , Urea resin, bismaleimide resin, polyester urethane resin, polyether urethane resin, and silicone resin. These resins may be used alone, or a plurality of resins may be used in combination.

  The polymerizable resin preferably used in the present invention is an epoxy resin, a (meth) acrylate resin polyurethane resin, a biodegradable resin such as polylactic acid, a polyvinyl alcohol resin, a urethane acrylate resin, or a polyolefin resin such as polypropylene or polyethylene.

  When an epoxy resin is used as the polymerizable resin C in the present invention, for example, bisphenol A, bisphenol F, bisphenol AD, bromine-containing bisphenol A, phenol novolac, cresol novolac, polyphenol, linear fat Glycidyl ether type epoxy resins such as aliphatic, butadiene and urethane types; hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, aromatic type, cycloaliphatic type, aliphatic glycidyl ester type epoxy resin; bisphenol type, ester Type, high molecular weight ether ester type, ether ester type, bromo type, novolac type, methyl-substituted epoxy resin; heterocyclic epoxy resin; triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, etc. Rishijiruamin type epoxy resins; epoxidized polybutadiene or linear aliphatic epoxy resin having an epoxy soybean oil and the like; cyclic aliphatic type epoxy resins, naphthalene-based novolak type epoxy resins, diglycidyl oxy naphthalene type epoxy resin. Among these, bisphenol A type, bisphenol F type, and bisphenol AD type glycidyl ether type epoxy resins are particularly preferable in view of performance and economy.

  In addition, additives such as a flexibilizer, a coupling agent, a flame retardant, a flame retardant aid, a colorant, and a filler, which are generally blended in the application field, are added to the epoxy resin as necessary. Further, it may be added within a range not impairing the performance of the present invention.

  When a liquid epoxy resin is added to the cured resin obtained by curing the resin composition of the present invention, the resin fluidity in a semi-cured state can be further improved. The liquid epoxy resin can also be used as a diluent because the handling property can be improved, such as being difficult to break and easy to slit.

  The liquid epoxy resin is not particularly limited as long as it is liquid. Examples of the polyfunctional liquid epoxy resin include Epicoat E152 [trade name, manufactured by Japan Epoxy Resin Co., Ltd.], Epicron N730-S [trade name, Dainippon Ink Industries Co., Ltd.] liquid phenol novolak type epoxy resin, Epicoat E827, Epicoat E828 [both trade names, manufactured by Japan Epoxy Resin Co., Ltd.] and other liquid bisphenol A type epoxy resins, Epicoat E806, Epicoat E807 Liquid bisphenol F type epoxy resin such as [Both trade name, manufactured by Japan Epoxy Resin Co., Ltd.], Epicoat E630 [trade name, manufactured by Japan Epoxy Resin Co., Ltd.], GOT, GAN [trade name, Nippon Kayaku Co., Ltd.] Liquid glycidylamine type epoxy resin, etc. -73 [trade name, Asahi Denka Kogyo Co., Ltd.] liquid urethane-modified bisphenol A type epoxy resin, YED122, YED111N [both trade names, manufactured by Japan Epoxy Resins Co., Ltd.] and other liquid epoxy such as monofunctional epoxy resin Resin.

  The epoxy resin preferably has a lower limit of epoxy value (also referred to as epoxy equivalent) of 150 or more, more preferably 170 or more, and most preferably 190 or more. The upper limit value of the epoxy value of the epoxy resin is preferably 700 or less, more preferably 500 or less, and most preferably 300 or less.

  When the epoxy value of the epoxy resin is less than 150, the number of polar groups in the cured resin obtained by curing the resin composition of the present invention increases, so that the dielectric properties may be impaired. That is, the cured resin may have a high dielectric constant and dielectric loss tangent. On the other hand, when the epoxy value exceeds 700, the crosslink density in the cured resin is lowered, so that the heat resistance may be impaired.

  Furthermore, in order to increase the crosslink density in the cured resin, it is preferable to use a polyfunctional epoxide compound as the polymerizable resin C. The polyfunctional epoxide that can be used in the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule, and can be appropriately selected depending on the application and purpose. Among these, preferred compounds are those having 2 to 6 epoxy groups in the molecule. Examples of the multifunctional epoxide compound (monomer) are structurally classified below.

(EP-1) Diglycidyl ether of divalent phenols Examples of the diglycidyl ether of divalent phenols include diglycidyl ethers of divalent phenols (C6-30). Diglycidyl ethers of dihydric phenols (C6-30) include, for example, bisphenol F, -A, -B, -AD and -S diglycidyl ether, halogenated bisphenol A diglycidyl ether (tetrachlorobisphenol A diglycidyl). Ether), catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl diglycidyl ether, tetramethyl Biphenyl diglycidyl ether, 9,9'-bis (4-hydroxyphenyl) fluorenediglycidyl ether, 2 mol of bisphenol A and 3 mol of epichlorohydrin It includes diglycidyl ethers obtained from the reaction.

(EP-2) Polyglycidyl ethers of polyhydric phenols having a valence of 3 or more Examples of polyglycidyl ethers of polyhydric phenols having a valence of 3 or more include pyrogallol triglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris ( Hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl-tert-butyl-butylhydroxymethane triglycidyl ether 4,4′-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-phenylethyl) L) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolac resin (Mn 400 to 5,000), glycidyl ether of limonene phenol novolac resin (Mn 400 to 5,000), phenol and glyoxal, Examples include glutaraldehyde or polyglycidyl ether of polyphenol (Mn 400 to 5,000) obtained by condensation reaction of formaldehyde, and polyglycidyl ether of Mn 400 to 5,000 polyphenol obtained by condensation reaction of resorcin and acetone.

(EP-3) Diglycidyl ether of aliphatic dihydric alcohol As diglycidyl ether of aliphatic dihydric alcohol, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, polyethylene glycol (Mn 150-4,000) diglycidyl ether, polypropylene glycol (Mn 180-5,000) diglycidyl ether, polytetramethylene glycol (Mn 200-5,000) diglycidyl ether, neopentyl Examples include glycol diglycidyl ether and diglycidyl ether of an adduct of bisphenol A alkylene oxide [EO or PO (1 to 20 mol)].

(EP-4) Polyglycidyl ether of trihydric or higher aliphatic alcohol As polyglycidyl ether of trihydric or higher aliphatic alcohol, for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, Examples include sorbitol hexaglycidyl ether and poly (n = 2 to 5) glycerol polyglycidyl ether.

(EP-5) Glycidyl ester type (i) Examples of glycidyl esters of aromatic polycarboxylic acids include glycidyl esters of phthalic acids. Examples of glycidyl esters of phthalic acids include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and trimellitic acid triglycidyl ester.
(Ii) Examples of the glycidyl ester of an aliphatic or alicyclic polycarboxylic acid include, for example, aromatic nucleated water additives of the above-mentioned phenolic glycidyl ester, dimer acid diglycidyl ester, diglycidyl oxalate, diglycidyl malate, di Glycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, glycidyl (meth) acrylate (co) polymer (degree of polymerization, for example, 2-10), tricarbyl acid triglycidyl ester Can be mentioned.

(EP-6) Glycidylamine type (i) Examples of glycidylamines of aromatic amines include N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetra. Examples include glycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyldiaminodiphenylsulfone, N, N, N ′, N′-tetraglycidyldiethyldiphenylmethane, and N, N, O-triglycidylaminophenol.
(Ii) Examples of glycidylamines of aliphatic amines include N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidylhexamethylenediamine.
(Iii) Examples of glycidylamines of alicyclic amines include hydrogenated compounds of N, N, N ′, N′-tetraglycidylxylylenediamine.
(Iv) Examples of the glycidylamine of the heterocyclic amine include trisglycidylmelamine.

(EP-7) Chain aliphatic epoxides Examples of chain aliphatic epoxides include, for example, epoxidized polybutadiene having an epoxy equivalent of 130 to 1,000 (Mn 90 to 2,500) and epoxidized soybean oil (Mn 130 to 2,500). Is mentioned.

(EP-8) Alicyclic Epoxides Examples of alicyclic epoxides include, for example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl. Ethers, 3,4 epoxy-6-methylcyclohexylmethyl 3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4 -Epoxy-6-methylcyclohexylmethyl) butylamine. Moreover, the nuclear hydrogenation thing of the epoxy compound of the said phenols is also included.

  These polyepoxy compounds can be used in combination of two or more. Of these, glycidyl ether type and glycidyl ester type are preferable.

  Examples of the oxetane compound include a C6-20 aliphatic oxetane compound (for example, 3-ethyl-3-hydroxymethyloxetane) and a C7-30 aromatic oxetane compound (for example, benzyloxetane and xylylenebisoxetane). C6-30 aliphatic carboxylic acid oxetane compound (for example, adipate bisoxetane), C8-30 aromatic carboxylic acid oxetane compound (for example, terephthalate bisoxetane), C8-30 alicyclic carboxylic acid oxetane Compounds (eg, bisoxetane cyclohexanedicarboxylate, 3,3 ′-[methylenebis (oxymethylene)] bis (7-oxabicyclo [4.1.0] heptane and 3,3 ′-[ethylidenebis (oxymethylene)] Bis (7-oxabicyclo [4. 0.0] heptane), aromatic isocyanate-based oxetane compounds (eg, MDI bisoxetane), C 2-20 sulfur-based oxetane compounds (eg, thiirane, 2-methylthiirane, 2,2-dimethylthiirane, 2-hexylthiirane and 2-phenylthiirane).

  Moreover, as polymeric resin C, a polyfunctional acrylic monomer or oligomer is mentioned, for example.

  Examples of the bifunctional acrylic monomer compound include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. , Polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol Di (meth) acrylate, trimethylolpropane di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobisphenol A, bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol di (meth) acrylate, hydroxypivalate ester neopentyl glycol compound And di (meth) acrylate monomers such as di (meth) acrylate and bis [(meth) acryloyloxypropyl] tetramethyldisiloxane, and divinylbenzene.

  Further, for example, (poly) oxyethylene (preferably polymerization degree = 4 to 20) di (meth) acrylate, (poly) oxypropylene (preferably polymerization degree = 4 to 15) di (meth) acrylate, polytetramethylene glycol (Preferably degree of polymerization = 4-12) di (meth) acrylate, (poly) oxyethylene (preferably degree of polymerization = 4-8) bisphenol A · di (meth) acrylate, (poly) oxypropylene (preferably polymerized) Degree = 4-6) Bisphenol A · di (meth) acrylate, (poly) oxyethylene (preferably degree of polymerization = 4-8) Hydrogenated bisphenol A · di (meth) acrylate and (poly) oxypropylene (preferably Is a degree of polymerization = 4-6) hydrogenated bisphenol A.di (meth) acrylate.

  Examples of the trifunctional acrylic monomer compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta (meth) acrylate. , Tris (2-hydroxyethylisocyanate) tri (meth) acrylate, tris (diethylene glycol) trimaleate tri (meth) acrylate, 3,7,14-tris [((((meth) acryloyloxypropyl) dimethylsiloxy)]-1 3,5,7,9,11,14-heptaethyltricyclo [7.3.3.15.11] heptasiloxane, 3,7,14-tris [(((meth) acryloyloxypropyl) dimethylsiloxy ]]-1,3 5,7,9,11,14-heptaisobutyltricyclo [7.3.3.15.11] heptasiloxane, 3,7,14-tris [(((meth) acryloyloxypropyl) dimethylsiloxy)]- 1,3,5,7,9,11,14-heptaisooctyltricyclo [7.3.3.15.11] heptasiloxane, 3,7,14-tris [(((meth) acryloyloxypropyl) Dimethylsiloxy)]-1,3,5,7,9,11,14-heptacyclopentyltricyclo [7.3.3.15.11] heptasiloxane and 3,7,14-tris [(((meta) Acryloyloxypropyl) dimethylsiloxy)]-1,3,5,7,9,11,14-heptaphenyltricyclo [7.3.3.15.11] heptasiloxane. It is.

  In addition, for example, glycidyl methacrylate, 2-methyl-glycidyl methacrylate, epoxidized isoprenyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, ethyl 2- (hydroxymethyl) acrylate, 1-allyl-2,3-epoxypropane , 2-acrylamido-2-methylpropanesulfonic acid, N, N′-diacryloyl-1,2-dihydroxyethylenediamine, 2-hydroxyethyl acrylate, N, N′-methylenebisacrylamide or N-acryloxysuccinimide A monomer is mentioned.

The resin composition of the present invention may contain a curing accelerator, an ultraviolet absorber or an antioxidant, and may further contain the following components.
(1) A powdery reinforcing agent or filler. For example, metal oxides such as high refractive index metal oxides such as zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), alumina (Al ₂ O ₃ ), nanosilica (SiO ₂ ) and zinc oxide (ZnO ₂ ), Examples thereof include silicon compounds such as finely divided silica, fused silica and crystalline silica, transparent fillers such as glass beads, metal hydroxides such as aluminum hydroxide, kaolin, mica, quartz powder, graphite and molybdenum disulfide. In particular, by adding nano silica, the absolute amount of the SiO ₂ component after the surface treatment can be increased and the surface can be changed to a more hydrophilic surface. These are mix | blended in the range which does not impair the transparency of the resin composition of this invention. A desirable ratio when blending these is a mass ratio with respect to the total amount of the resin composition of the present invention, and is in a range of 0.10 to 1.0.

(2) Colorant or pigment. Examples include titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red, and organic dyes.
(3) Flame retardant. For example, antimony trioxide, a bromine compound, and a phosphorus compound are mentioned.
(4) Ion adsorbent.
A desirable ratio when these components are blended is 0.0001 to 0.30 in terms of mass ratio with respect to the total amount of the resin composition.
(5) A silane coupling agent that does not contain epoxy or oxetanyl in the molecule.
(6) A nanoparticle dispersion of a metal oxide such as zirconia, titania, alumina or silica.

  A desirable ratio when blending these components (1) to (6) is 0.01 to 0.50 in terms of mass ratio to the total amount of the resin composition.

  The resin composition of the present invention includes a structural unit A derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule and a plurality of polymerizable functional groups in the molecule. A resin composition comprising at least one selected from structural units B derived from a silsesquioxane having a group and a polymerizable resin C, and the structure of the resin is a block copolymer or a random copolymer However, it is necessary to have a crosslinked structure.

  In the resin composition of the present invention, the mass ratio of the structural unit A, the structural unit B, and the polymerizable resin C is (A) :( B) = 0: 100 to 100: 0, (B) :( C) = 5: It is preferably in the range of 95 to 99: 1. When a plurality of types of monomer compounds are used, the ratio of each monomer may be appropriately determined according to the characteristics of the target resin composition. On the other hand, in order to make the resin composition into a film and make the surface hydrophilic in a short time, the mass ratio of the structural unit A and / or the structural unit B containing silsesquioxane is set to the total mass of the resin composition. It is preferably maintained in the range of 10 to 80 parts, more preferably 20 to 80 parts.

  The mass ratio of the polymerizable resin C contained in the resin composition of the present invention is not particularly limited, but in order to obtain a cured film having a hydrophilic surface, a polyfunctional epoxide or a hydrophilic polyfunctional acrylic compound is used. It is preferable to select it as a co-component of the resin composition.

  The resin composition of the present invention may further contain a diluent.

  As the diluent, an organic solvent, a liquid epoxy compound containing no silicon atom in the molecule, or a liquid oxetane compound containing no silicon in the molecule can be used. In the present invention, compounds each having two or more functional groups in one molecule may be referred to as epoxy resin or oxetane resin.

  As the diluent, it is preferable to use an epoxy resin that does not contain a silicon atom in the molecule or an oxetane resin that does not contain silicon in the molecule because the organosilicon compound of the present invention is cured by the curing agent.

  Specific examples of the epoxy resin containing no silicon atom in the molecule include epoxy resins such as bisphenol-A type, bisphenol-F type, bisphenol-S type, hydrogenated bisphenol-A type, Daicel Chemical Industries, Ltd. And alicyclic epoxy resins such as Celoxide (trade name) 2021P, Celoxide (trade name) 3000, and Celoxide (trade name) 2081.

  Specific examples of the oxetane resin that does not contain silicon in the molecule include oxetane resins such as Aron Oxetane (registered trademark) manufactured by Toagosei Co., Ltd. Moreover, the silane coupling agent which contains an epoxy or oxetanyl in a molecule | numerator is mentioned. Specific examples of the silane coupling agent include silane coupling agents such as Silac Ace (trade name) S510, S520, and S530 manufactured by JNC Corporation.

  The weight average molecular weight of the resin composition of the present invention is 1000 to 1,000,000 although it varies depending on the content of the structural unit C and the like. On the other hand, the molecular weight distribution (Mw / Mn) of the polymer of the present invention is about 1.01 to 2.5.

  The method for adjusting the resin composition varies depending on the types of the structural unit A to the structural unit B, their ratios, and the properties of the target resin composition, but in view of simplicity and versatility, radical polymerization or cationic polymerization is cured. It is preferable to employ a part of the process. In addition, radical polymerization and cationic polymerization may be employed in stages. In the present invention, it is preferable to use a cationic polymerization initiator in the initial stage of the curing process.

  Examples of the cationic polymerization initiator include an active energy ray cationic polymerization initiator that generates a cationic species or a Lewis acid by active energy rays, and a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heat.

  Examples of the active energy ray cationic polymerization initiator include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,586,616). ), Aryldiazonium compounds (US Pat. No. 3,708,296), aromatic onium salts of group VIa elements (US Pat. No. 4,058,400), aromatic onium salts of group Va elements (US Pat. No. 4,069,055) ), Dicarbonyl chelates of group IIIa-Va elements (US Pat. No. 4068091), thiopyrylium salts (US Pat. No. 4,139,655), group VIb elements in the form of MF6-anions (US Pat. No. 4,161,478) M is selected from phosphorus, antimony and arsenic Arylsulfonium complex salts (US Pat. No. 4,231,951), aromatic iodonium complex salts and aromatic sulfonium complex salts (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide- Bis-hexafluorometal salts [Journal of Polymer Science, Polymer Chemistry, Vol. 2, Item 1789 (1984)]. Other examples include mixed ligand metal salts of iron compounds and silanol-aluminum complexes.

  Examples of preferred active energy ray cationic polymerization initiators are arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, Group V and Group VI elements. Some of these salts are commercially available.

  As the thermal cationic polymerization initiator, for example, a cationic or protonic acid catalyst such as a triflic acid salt, boron trifluoride or the like is used. Preferable examples of the thermal cationic polymerization initiator include triflate.

  Examples of the triflate include diethylammonium triflate, diisopropylammonium triflate, and ethyldiisopropylammonium triflate.

  On the other hand, among aromatic onium salts that are also used as active energy ray cationic polymerization initiators, there are those that generate cationic species by heat, and these can also be used as thermal cationic polymerization initiators.

  Among these cationic polymerization initiators, aromatic onium salts are preferable because they are easy to handle and have a good balance between latency and curability. Among them, diazonium salts, iodonium salts, sulfonium salts, and phosphonium salts are handled. It is preferable in that it has an excellent balance between property and potential. A cationic polymerization initiator can be used individually or in combination of 2 or more types.

  A preferable use ratio of the cationic polymerization initiator is 0.0005 to 0.05 in terms of mass ratio with respect to the total amount in terms of epoxy resin to be used.

  When the resin composition of the present invention comprising at least one of the structural unit A and the structural unit B and the polymerizable resin C is produced from a radical polymerizable monomer, it may be carried out using a radical polymerization initiator. it can.

  Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), dimethyl Azo compounds such as -2,2'-azobisisobutyrate and 1,1'-azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di- peroxides such as t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyneodecanoate; and tetraethylthiuram And dithiocarbamates such as disulfides. .

  Furthermore, examples of the polymerization reaction include living radical polymerization and active energy ray polymerization.

  In the present invention, the active energy ray refers to an energy ray that can generate an active species by decomposing a compound that generates an active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays, and electron rays.

  A specific example of the active energy ray polymerization initiator is not particularly limited as long as it is a compound that generates radicals upon irradiation with ultraviolet rays or visible rays. Examples of the compound used as the active energy ray polymerization initiator include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone and isopropylxanthone.

  A film comprising the resin composition of the present invention and a molded article having the film are obtained by a step of forming a film on the substrate from the resin composition of the present invention, a step of curing the film, and a surface treatment step of the film. . The film can be formed by, for example, coating, and the film can be usually cured by one or more of drying, heating, and active energy ray irradiation.

  The method for applying the solution containing the resin composition of the present invention to the substrate is not particularly limited. For example, spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, reverse coating Method, rod coating method, bar coating method, die coating method, kiss coating method, reverse kiss coating method, air knife coating method and curtain coating method.

  Examples of substrates to be applied include transparent glass substrates such as white plate glass, blue plate glass, and silica-coated blue plate glass; polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, triacetate, diacetate Synthetic resin sheet, film, etc .; cycloolefin resin containing norbornene resin (for example, trade name: ZEONOR, ZEONEX, Nippon Zeon Co., Ltd., trade name: ARTON, manufactured by JSR Corporation), methacrylstyrene, polysulfone, Transparent resin substrate used for optical applications such as alicyclic acrylic resin or polyarylate; metal substrate such as aluminum plate, copper plate, nickel plate or stainless steel plate; other ceramic plate, semiconductor substrate having photoelectric conversion element; urethane rubber, Chirengomu and the like.

  These substrates may be pretreated. Examples of the pretreatment include chemical treatment using a silane coupling agent, sand blast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, and vapor phase. Reaction methods and vacuum deposition are mentioned. The applied solution can be dried in an environment of room temperature to about 200 ° C.

  When an active energy ray polymerization initiator is used, it can be cured by irradiating a photoactive energy ray or an electron beam with an active energy ray source after coating and drying.

  As the active energy ray source, depending on the nature of the active energy ray polymerization initiator used, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, a solid laser and an electron beam irradiation. Apparatus.

  Next, the molded body is surface-treated by irradiating the coated molded body substrate surface with high energy rays. As the surface treatment, at least one treatment selected from ozone treatment and ultraviolet irradiation treatment is preferable. As the ultraviolet irradiation treatment, irradiation with deep energy (UV) with high energy is preferable, and a low pressure mercury lamp emitting 185 nm and 254 nm and a xenon excimer lamp emitting 172 nm are generally used as a light source.

  When the energy of the irradiated UV light is higher than the molecular bond energy of the organic compound, the probability that the molecular bond is broken increases, but since deep ultraviolet rays with a wavelength of 240 nm or less decompose oxygen, the 172 nm and 185 nm lines absorb ozone from oxygen. Generate.

  Deep ultraviolet rays of 254 nm decompose ozone and produce high energy active oxygen. When the C—H bond is broken, the H atom is immediately extracted. The active oxygen reacts with the organic compound to form an oxygen-rich functional group such as CO or CO (OH) on the surface, or to decompose the functional group of the compound. In other words, oxygen radicals have polarity, can increase surface energy, increase hydrophilicity, and strengthen adhesive force depending on hydrophilicity.

  The resin composition containing the silsesquioxane derivative of the present invention uses silica as a part of the silsesquioxane structure. Examples of the high energy rays used here include an electron beam, an ultraviolet ray, an X-ray, Infrared and microwave. Among these, ultraviolet rays are preferable, and deep ultraviolet rays which are generally ultraviolet rays having a wavelength range of 200 to 350 nm are more preferable because they generate ozone.

  High energy ray irradiation is preferably performed in air or in an oxygen gas-containing gas. Examples of gases other than oxygen gas include nitrogen gas and argon gas. The temperature at the time of irradiation with high energy rays and the conversion temperature to silica are preferably temperatures at which scattering of the low molecular weight silsesquioxane resin can be suppressed as much as possible, and preferably within a range of 10 to 50 ° C.

  In order to obtain a cured product having a hydrophilic surface, various raw materials can be selected as described above, and various processes can be employed. In the present invention, a cured product can be prepared by the following processes. preferable.

(1) A silsesquioxane not containing the structural unit A and / or fluorosilsesquioxane derived from fluorosilsesquioxane having an addition polymerizable functional group and having a plurality of polymerizable functional groups in the molecule A resin composition comprising at least one selected from the derived structural unit B and a polymerizable resin C (for example, a polyfunctional monomer) is stirred and mixed, and a cationic polymerization initiator is added, preferably at room temperature to 50 ° C. Mix and dissolve.
(2) After mixing and dissolving, depressurize and degas. Then, the mixture is spin-coated on a substrate such as glass, (a) a thermal cationic curing agent (cationic polymerization initiator) is added as a curing agent, preferably heated at 80 to 100 ° C., preferably for 5 to 20 minutes, and finally It is preferably cured by heating at 120 to 160 ° C., preferably for 30 to 60 minutes, or (b) a photocationic curing agent (cationic polymerization initiator) is added, preferably for 0.1 to 60 minutes, It hardens | cures preferably by exposing the ultraviolet-ray (i line | wire) of 50-2000mJ / cm < ² >.
(3) A cured product having a hydrophilic surface can be obtained by subjecting the produced cured product to surface treatment by irradiation with deep ultraviolet rays.

  As a result, a cured product having a water contact angle of less than 10 ° C. is obtained. In particular, the mass ratio of the structural unit A and / or the structural unit B containing silsesquioxane is preferably 10 to 80 with respect to the total mass of the resin composition. Part, more preferably 20 to 80 parts, a cured product having a superhydrophilic surface with a contact angle in the range of 0.1 to 5 ° is realized.

  A cured product having a functional surface obtained by surface-treating the resin composition of the present invention is obtained. Functional surfaces include superhydrophilic surfaces, gas barrier layers, hard coat layers, or heat resistant surfaces.

A super-hydrophilic surface refers to a surface with a water contact angle of less than 10 °. The gas barrier layer refers to a layer having a water vapor transmission rate of 10 ⁻² g / m ² · 24 hr or less. A hard-coat layer means the layer which is more than H in the pencil hardness test measured based on JISK5600-5-4 (1999). The heat-resistant surface refers to a surface that can achieve a glass transition temperature of 200 ° C. or higher and a linear expansion coefficient of 50 ppm / K or lower as thermal characteristics as a film or composition.

  The cured product of the present invention as described above is excellent in flattening property on the substrate, excellent in embedding in the step of the substrate of the electronic device having an exterior structure, and is electrically insulating after irradiation with high energy rays. Since it becomes an excellent silica thin film, it is particularly useful as an application requiring such characteristics, for example, an interlayer insulating film of a multilayer semiconductor device, and an electronic material.

  Hereinafter, the present invention will be described in more detail based on examples, but the scope of the present invention is not limited thereto.

Example 1
In a screw tube, 1.8 g of silsesquioxane derivative B “described as (1-1)” described in [Synthesis Example 1] of Japanese Patent Application Laid-Open No. 2009-167390, and epoxy resin as polymerizable resin C [Celoxide CEL2021P (trade name: Daicel Corporation)] 7.3 g and a mixture of 2,2-bis (4-glycidyloxyphenyl) propane (Tokyo Kasei) 0.9 g were added and stirred at 70 ° C. for 20 minutes. Next, the thermal cationic polymerization initiator Sun-Aid SI-100, 50 mg, was added and dissolved as a curing agent. The screw tube was set in a rotation / revolution mixer [Shinky Co., Ltd. Awatori Nerita ARE-250 (trade name)], mixed and defoamed to obtain a resin composition. The composition of the resin composition is shown in Table 1.
・ [Sun-Aid SI-100 (trade name: manufactured by Sanshin Chemical Industry Co., Ltd.)] (aromatic sulfonium type cationic polymerization initiator)
[[Celoxide CEL2021P (trade name; Daicel Industries)] (3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate)

  Next, the resin composition was coated on a glass substrate (40 mm × 40 mm) with a spin coater (500 rpm, 30 seconds) to a thickness of 150 μm so that no bubbles would enter, and 100 ° C. for 20 minutes and 150 ° C. for 30 minutes. The cured product was obtained by heating in the order of minutes.

Deep ultraviolet light (wavelength 185/254 nm, illuminance 14.6 mW / cm ² ) was irradiated on the surface of the cured product with a PHOTO SURFACE PROCESSOR [PL2003N-12 manufactured by Sen Special Light Source Co., Ltd.] at a distance of 10 mm, 0, 1, 2 Irradiated for 5 and 10 minutes, and each water contact angle was measured. The water contact angle was measured by using a contact angle measuring device (DropMaster DM500, manufactured by Kyowa Interface Science Co., Ltd.), dropping 1.8 μL of water on the surface of the cured resin film, and then changing the water contact angle by changing the position where the water was dropped. The average value was obtained by measuring points. The contact angle was measured on the day of irradiation with deep ultraviolet rays in order to suppress the influence of the surface condition due to aging. The results are shown in Table 2.

(Comparative Example 1)
A mixture of polymerizable resin C (Celoxide CEL2021P; 8.9 g, 2,2-bis (4-glycidyloxyphenyl) propane; 1.1 g) was added, stirred and dissolved by heating, and then thermal cationic polymerization was started as a curing agent. 50 mg of the agent (Sun-Aid SI-100) was added and dissolved. The screw tube was set in a rotation / revolution mixer [Shinky Co., Ltd. Awatori Nerita ARE-250 (trade name)], mixed and defoamed to obtain a resin composition. The composition of the resin composition is shown in Table 1.

In the same manner as in Example 1, heat curing was performed to obtain a sample of Comparative Example 1. Thereafter, as in Example 1, deep ultraviolet rays (185/254 nm, illuminance 14.6 mW / cm ² ) were irradiated at a distance of 10 mm for 1, 2, 5, and 10 minutes, and the respective water contact angles were measured. The contact angle measurement was performed on the day of irradiation with deep ultraviolet rays in order to suppress the influence of the surface state due to aging. The results are shown in Table 2.

  From the results shown in Table 2, the cured product of Example 1 containing the silsesquioxane derivative B (1-1) in the present invention is hydrophilic in comparison with the cured product of Comparative Example 1 that does not contain it by deep ultraviolet irradiation. In terms of sex, it showed a clear advantage in a short time.

  Therefore, when creating a curable film, the resin composition is heated and pre-cured with a cationic polymerization initiator or radical polymerization initiator, then crosslinked and cured by heat or energy ray irradiation at a higher temperature, and finally irradiated with deep ultraviolet rays. Thus, it was found that the surface treatment improves the coating strength, and a functional film having a superhydrophilic surface can be obtained in a short time.

  Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2013-012113) for which it applied on January 25, 2013, The whole is used by reference.

  The cured product obtained by surface-treating the resin composition of the present invention is excellent in hydrophilicity, thermal stability, physical strength, uniformity, surface characteristics, etc., and applied to gas barrier films or electronic materials. There is expected.

Claims (20)

  A structural unit A derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, and a silsesquioxane not containing fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule Hardened | cured material with the functional surface obtained by surface-treating the monomer composition which provides the at least 1 type of structural unit chosen from the derived structural unit B, and the resin composition which consists of polymerizable resin C. The cured product according to claim 1, wherein the fluorosilsesquioxane having one addition polymerizable functional group is represented by the following formula (1).

In formula (1), R _f ^{1 to} R _f ⁷ are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is fluorine or trifluoro A fluoroaryl having 6 to 20 carbon atoms replaced by methyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl is replaced by fluorine or trifluoromethyl, and A ¹ is An addition polymerizable functional group is shown. R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl. Or a cured product according to claim 2, which represents tridecafluoro-1,1,2,2-tetrahydrooctyl. The cured product according to claim 2, wherein A ¹ in the formula (1) is a radical polymerizable functional group. The cured product according to claim 4, wherein A ¹ in the formula (1) contains (meth) acryl or styryl. The cured product according to claim 5, wherein A ¹ in the formula (1) is represented by the following formula (3) or (5).

In the formula (3), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ⁶ is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, and in the formula (5), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms. In the formula (3), Y ¹ represents an alkylene having 2 to 6 carbon atoms, R ⁶ represents hydrogen or methyl, and in the formula (5), Y ² represents a single bond or an alkylene having 1 or 2 carbon atoms. The cured product according to claim 6. The structural unit B derived from silsesquioxane not containing the fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule contains at least one silsesquioxane derivative represented by the following structure. The cured product according to claim 1.

In the formula (A-1) to the formula (A-3), each R is independently hydrogen, a non-adjacent —CH ₂ — may be replaced with —O— or cycloalkylene, and the carbon number is 1 to 45 Alkyl, cycloalkyl having 4 to 8 carbon atoms, or substituted or unsubstituted aryl. In the substituted benzene ring, any hydrogen may be replaced with alkyl having 1 to 10 carbon atoms or halogen. R ¹ is a group independently selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl. At least one X is a group having hydrogen or a polymerizable functional group, and the remaining X is a group defined in the same manner as R ¹ .   The hardened | cured material of Claim 8 whose R is a phenyl group or a cyclohexyl group in said Formula (A-1)-Formula (A-3). The cured product according to claim 8, wherein X is a group represented by any one of formula (2), formula (3), formula (4) and formula (5).

The structural unit B derived from silsesquioxane not containing the fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule is a silsesquioxane derivative represented by the following formula (1-1): Item 11. A cured product according to item 8.

  The cured product according to any one of claims 1 to 11, wherein the polymerizable resin C is at least one resin selected from a thermoplastic resin, a thermosetting resin, and / or an active energy ray curable resin.   The polymerizable resin C is (meth) acrylate resin, polyurethane resin, biodegradable resin, polyvinyl alcohol resin, urethane acrylate resin, polyolefin resin, epoxy resin not containing silicon in the molecule, and oxetane not containing silicon in the molecule. It is at least 1 or more types of resin chosen from resin, The hardened | cured material of any one of Claims 1-12.   The cured product according to claim 1, wherein the surface treatment is an ozone treatment and / or an ultraviolet irradiation treatment.   The cured product according to claim 1, wherein the functional surface provided by the surface treatment is a superhydrophilic surface.   The cured product according to claim 1, wherein the functional surface provided by the surface treatment is a gas barrier layer.   The hardened | cured material of Claim 1 whose said functional surface provided by the said surface treatment is a hard-coat layer.   The hardened | cured material of Claim 1 whose said functional surface provided by the said surface treatment is a heat resistant surface.   A structural unit A derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, and a silsesquioxane not containing fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule A film, a coating film, or a molded body produced from a resin composition comprising a monomer compound that provides at least one structural unit selected from the derived structural unit B and a polymerizable resin C.   A structural unit A derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, and a silsesquioxane not containing fluorosilsesquioxane and having a plurality of polymerizable functional groups in the molecule A resin composition comprising a monomer compound giving at least one structural unit selected from the derived structural unit B and a polymerizable resin C, wherein the resin composition is cured and surface-treated (film) in contact with the surface A resin composition having an angle of less than 10 °.