TW201444924A - Hardened material, film, coating film, compact and resin composition - Google Patents

Abstract

This invention relates to a cured material having a functional surface obtained by conducting a surface treatment on the following resin composition. The resin composition includes at least one selected from a constitutional unit A derived from a fluorosilsesquioxane having one addition polymerizable functional group in the molecule and a constitutional unit B derived from a silsesquioxane having multiple polymerizable functional groups in the molecule, whereas the silsesquioxane does not contain the fluorosilsesquioxane, and polymerizable resin C.

Description

Hardened material, film, coated film, formed body, and resin composition

The present invention relates to a resin composition useful as an optical material, an electrical insulating material, or the like obtained as a coating material. Further, the present invention relates to a molded body having a surface modified with a resin composition containing a fluorine-based polymer.

In recent years, light-emitting devices such as light-emitting diodes (LEDs) that have been put into practical use in various display panels, light sources for image reading, traffic signals, large-sized display units, backlights for mobile phones, and the like have generally been borrowed. It is produced by resin sealing by using an alicyclic acid anhydride as a curing agent for an aromatic epoxy resin. However, it is known that the acid anhydride of the resin is easily discolored by an acid or hardens for a long time. Further, in the case where 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 is yellowed.

In order to eliminate such a problem, attempts have been made to use a cyclic aliphatic epoxy resin or an acrylic resin, and to carry out a resin such as an LED by a cationic polymerization initiator. Method of sealing (refer to Patent Document 1 and Patent Document 2). However, since the hardened resin subjected to the above cationic polymerization is very brittle, cracking damage is likely to occur due to thermal cycle, and the color of the sealing resin after curing is significantly higher than that of the conventional aromatic epoxy resin-anhydride curing system. This major shortcoming. Therefore, the cured resin is not suitable for applications requiring colorless transparency, and particularly for sealing of LEDs requiring heat resistance and transparency.

Therefore, in Patent Document 3, there is disclosed a problem caused by a thermal cycle. A resin composition for an LED sealing material which is improved in crack generation and excellent in light resistance. The resin composition shown here is a hydrogenated epoxy resin or an alicyclic epoxy resin as a matrix component, but the change with time after hardening is still large, and further quality stability is desired.

On the other hand, Patent Document 4 describes a method for filling a wiring base. An embedding resin composition in which a gap between an electronic component of the board and the substrate is used, and the embedding resin composition uses an aliphatic cyclic epoxy resin or an oxetane resin as a low viscosity agent. However, this resin composition contains a large amount of inorganic filler, and cannot be applied to a field requiring transparency.

In addition, Patent Document 5 discloses a modified oxetane tree A resin composition which is soluble in an alkaline aqueous solution of an active energy ray-curable resin, and the resin composition shown here is intended to be an alkali-soluble resin, and modified oxetane resin or polyfunctional Since the oxetane resin has an unsaturated bond, discoloration caused by the thermal history cannot be avoided.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1]: Japanese Patent Laid-Open No. 61-112334

[Patent Document 2]: Japanese Patent Laid-Open No. 02-289611

[Patent Document 3]: Japanese Patent Laid-Open Publication No. 2003-277473

[Patent Document 4]: Japanese Patent Laid-Open Publication No. 2004-27186

[Patent Document 5]: International Publication No. 2001/072857

[Patent Document 6]: Japanese Patent Laid-Open Publication No. 2006-070049

[Patent Document 7]: International Publication No. 2004/081084

[Patent Document 8]: Japanese Patent Laid-Open Publication No. 2004-331647

[Patent Document 9]: International Publication No. 2003/24870

[Patent Document 10]: International Publication No. 2004/24741

[Patent Document 11]: International Publication No. 2008/72765

[Patent Document 12]: Japanese Patent Laid-Open Publication No. 2009-114409

[Patent Document 13]: Japanese Patent Laid-Open Publication No. 2012-46752

An object of the present invention is to provide a curable resin composition which can be exposed to light by ultraviolet light or electron beam to form a cross-linking group in a copolymer to form a network polymerization. A network polymer is obtained to obtain a solvent-insoluble ultra-thin film, and a protective film for various optical elements, magnetic heads, and the like, surface modification, and surface treatment of various materials can be performed.

As a result of intensive studies, the present inventors have found that by subjecting the following resin composition to surface treatment, the film strength can be improved, and in a short time. The present invention has been completed by a functional film having a superhydrophilic surface containing a constituent unit A selected from a fluorosilsesquioxane having an addition polymerizable functional group in a molecule, and a source thereof. At least one of the constituent units B of the sesquioxane having no fluorine-containing sesquioxane and having a plurality of polymerizable functional groups in the molecule, and the polymerizable resin C.

That is, the present invention is as follows.

(1) A cured product having a functional surface obtained by subjecting a resin composition to a surface treatment, the resin composition comprising a monomer compound providing at least one constituent unit selected from the group consisting of the constituent unit A and the constituent unit B And the polymerizable resin C, the structural unit A is derived from a fluorosilsesquioxane having an addition polymerizable functional group in the molecule, and the above-mentioned constituent unit B is derived from fluorine-free sesquioxane and has a large amount in the molecule. A sesquioxane of a polymerizable functional group.

(2) The cured product according to the above (1), wherein the above-mentioned fluorosilsesquioxane having an addition polymerizable functional group is represented by the following formula (1).

In the formula (1), R _f ¹ to R _f ⁷ each independently represent an arbitrary methylene group which may be substituted by oxygen with a fluoroalkyl group having 1 to 20 carbon atoms and at least one hydrogen substituted by fluorine or trifluoromethyl group. a fluoroaryl group having 6 to 20 carbon atoms or at least one hydrogen in the aryl group substituted with fluorine or a trifluoromethyl group having 7 to 20 carbon atoms, and A ¹ representing an addition polymerization functional group base.

(3) The cured product according to the above (2), wherein R _f ¹ to R _f ⁷ in the above formula (1) independently represent 3,3,3-trifluoropropyl, 3,3,4, 4,5,5,6,6,6-nonafluorohexyl, or tridecafluoro-1,1,2,2-tetrahydrooctyl.

(4) or (3) wherein said cured product (1) in the above-mentioned formula A ¹ is a radical polymerizable functional group of the above (2),.

(5) The cured product according to the above (4), wherein A ¹ in the above formula (1) contains a (meth)acrylic group or a styryl group.

(6) The cured product according to the above (5), wherein A ¹ in the above formula (1) is represented by the following formula (3) or formula (5).

In the above formula (3), Y ¹ represents an alkylene group having 2 to 10 carbon atoms, R ⁶ is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and the above formula ( In 5), Y ² represents a single bond or an alkylene group having a carbon number of 1 to 10.

(7) The cured product according to the above (6), wherein, in the formula (3), Y ¹ represents an alkylene group having 2 to 6 carbon atoms, and R ⁶ represents hydrogen or a methyl group, and the above formula (5) Y ² represents a single bond or an alkylene group having a carbon number of 1 or 2.

(8) The cured product according to the above (1), wherein the constituent unit B derived from the sesquioxane having no fluorine-containing sesquioxane and having a plurality of polymerizable functional groups in the molecule contains the following At least one sesquiterpene derivative represented by the structure.

[Chemical 3]

In the formulae (A-1) to (A-3), R is independently hydrogen, and the non-contiguous -CH ₂ - may be an alkyl group having 1 to 45 carbon atoms which may be substituted by -O- or a cycloalkyl group. A cycloalkyl group having 4 to 8 carbon atoms or a substituted or unsubstituted aryl group. In the benzene ring of the substituted aryl group, any hydrogen may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen. R ^{1 is} each independently a group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, and a phenyl group. At least one of X is hydrogen or a polymerizable functional group, and the remaining X is a group defined in the same manner as R ¹ .

(9) The cured product according to the above (8), wherein, in the formula (A-1) to the formula (A-3), R is a phenyl group or a cyclohexyl group.

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

(11) The cured product according to the above (8), wherein the above-mentioned sesquiterpene oxide derived from a fluorine-free sesquioxane having a plurality of polymerizable functional groups in the molecule The unit B is a sesquiterpene oxide derivative represented by the following formula (1-1).

The cured product according to any one of the above-mentioned (1), wherein the polymerizable resin C is selected from the group consisting of a thermoplastic resin, a thermosetting resin, and/or an active energy ray-curable resin. More than one resin.

(13) The cured product according to any one of the above (1), wherein the polymerizable resin C is selected from the group consisting of (meth) acrylate resins, polyurethane resins, and biodegradation. At least one or more of a resin, a polyvinyl alcohol resin, an urethane urethane resin, a polyolefin resin, an epoxy resin containing no antimony in the molecule, and an oxetane resin containing no antimony in the molecule.

(14) The cured product according to the above (1), wherein the surface treatment is ozone treatment and/or ultraviolet irradiation treatment.

(15) The cured product according to the above (1), wherein the functional surface imparted by the surface treatment is a superhydrophilic surface.

(16) The cured product according to (1) above, wherein the surface treatment is performed by the above The above functional surface imparted is a gas barrier layer.

(17) The cured product according to (1) above, wherein the functional surface imparted by the surface treatment is a hard coat layer.

(18) The cured product according to the above (1), wherein the functional surface imparted by the surface treatment is a heat resistant surface.

(19) A film, a coating film or a molded body produced from a resin composition containing a monomer compound which provides at least one constituent unit selected from the constituent unit A and the constituent unit B, and a polymerizable property Resin C, the above-mentioned structural unit A is derived from a fluorosilsesquioxane having an addition polymerizable functional group in the molecule, and the above-mentioned constituent unit B is derived from a fluorine-free sesquioxane and has a plurality of polymerizable functionalities in the molecule. A sesquiterpene oxide.

(20) A resin composition comprising a monomer compound which provides at least one structural unit selected from the group consisting of the structural unit A and the structural unit B, and a polymerizable resin C, wherein the constituent unit A is derived from a fluorosilsesquioxane having an addition polymerizable functional group in the molecule, and the above-mentioned constituent unit B is derived from a sesquioxane having no fluorinated sesquioxane and having a plurality of polymerizable functional groups in the molecule, and The contact angle of the (film) surface obtained by hardening and surface-treating the above resin composition was less than 10°.

The resin composition of the present invention comprises at least one selected from the group consisting of the structural unit A and the constituent unit B, and the polymerizable resin C, which is derived from a fluorosilsesquioxane having an addition polymerizable functional group in the molecule. , the above constituent unit B is derived from a sesquioxane having no fluorine sesquioxane and having a plurality of polymerizable functional groups in a molecule, the resin composition being cracked by bonding between an organic group and a ruthenium atom by deep ultraviolet rays or ozone, and oxygen Since the atom is bonded to the cleavage portion, whereby a decane bond can be formed, a surface film can be obtained by surface treatment, and a functional film having a super-hydrophilic surface in a short time can be obtained. The cured product obtained by subjecting the resin composition of the present invention to surface treatment 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 is a cured product having a functional surface obtained by surface-treating a resin composition containing at least one selected from the group consisting of the constituent unit A and the constituent unit B, and polymerizability. In the resin C, the above-mentioned structural unit A is derived from a fluorosilsesquioxane having an addition polymerizable functional group, and the above-mentioned constituent unit B is derived from a fluorine-free sesquioxane-free compound and has a plurality of polymerizable functional groups in the molecule. Semi-oxane.

In the present invention, the addition polymerizable functional group means a functional group capable of undergoing addition polymerization, and the term "derived from" means a polymerization 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 constituent unit B in the resin composition is represented by b, and the resin composition is represented by c. The molar fraction (%) of the polymerizable resin C satisfies 0 < a < 100, 0 < b < 100, 0 < c < 100, and a + b + c = 100, respectively.

In the present invention, the term "polymerizable resin C" means high molecular weight. A general term for a polymerizable resin and a polymerizable oligomer having a weight average molecular weight of several hundred to several thousands and a polymerizable monomer.

The resin composition of the present invention can be made, for example, by having one addition in the molecule a fluorosilsesquioxane which is a polymerizable functional group, and a sesquioxane having no fluorosesquioxanes having an addition polymerizable functional group and having a plurality of polymerizable functional groups in the molecule, and an addition The polymerizable monomer (polymerizable resin C) is obtained by copolymerization.

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

The fluorosesquioxanes have a sesquiterpene skeleton in the molecular structure. The sesquioxane is a general term for a polyoxyalkylene represented by [(R-SiO _1.5 )n] (R is an arbitrary substituent). The structure of the sesquiterpene oxide corresponds to its Si-O-Si skeleton, and is generally classified into a random structure, a trapezoidal structure, and a cage structure. Further, the cage structure is classified into a T8 type, a T10 type, a 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 of sesquiterpene oxide [(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, and a cationically polymerizable functional group such as a vinyl ether, a propenyl ether or an epoxy group. a group having an anion polymerizable functional group such as a vinyl carboxyl group or a cyanoacryl fluorenyl group. A group having a cationically polymerizable functional group such as an epoxy group or a radical polymerizable functional group is preferred.

As the above radical polymerizable functional group, as long as it is subjected to radical polymerization The base is not particularly limited, and examples thereof include a methyl methacrylate group, an acryl fluorenyl group, an allyl group, a styryl group, an α-methylstyryl group, a vinyl group, a vinyl ether, a vinyl ester, and the like. Acrylamide, methacrylamide, N-vinylamine, maleate, fumarate and N-substituted maleimide. Among them, a group containing a (meth)acrylic group or a styryl group is preferred. Here, the (meth)acrylic group means a general term of an acryl group and a methacryl group, and represents an acryl group and/or a methacryl group. The same is true below.

The radical polymerizable functional group having the above (meth)acrylic group may, for example, be a group represented by the following formula (3).

In the formula (3), Y ¹ represents an alkylene group having a carbon number of 2 to 10, preferably an alkylene group having a carbon number of 2 to 6, more preferably an alkylene group having a carbon number of 3 (extended polypropylene) base). Further, R ⁶ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen or methyl. Here, the alkyl group having 1 to 5 carbon atoms may be either linear or branched. Further, examples of the radical polymerizable functional group having the above styryl group include the group represented by the following formula (5). In the formula (5), Y ² represents a single bond or an alkylene group having a carbon number of 1 to 10, preferably a single bond or an alkylene group having a carbon number of 1 to 6, more preferably a single bond or a carbon number. The alkylene group is 1 or 2, and particularly preferably represents a single bond or an alkylene group having a carbon number of 2 (extended ethyl group). Further, the vinyl group is bonded to any carbon of the benzene ring, preferably to the carbon bonded to the opposite side with respect to Y ² .

[Chemical 6]

The above fluorine silsesquioxane is characterized by having at least one fluoroalkyl group, fluoroarylalkyl group, or fluoroaryl group. In other words, one or more Rs of sesquiterpene oxide (R-SiO _1.5 )n are preferably fluoroalkyl groups, fluoroarylalkyl groups and/or fluoroaryl groups other than the above-mentioned addition polymerizable functional groups. base.

The fluoroalkyl group may be either linear or branched. The fluoroalkyl group has a carbon number of from 1 to 20, preferably from 3 to 14. Further, any methylene group of the fluoroalkyl group may be substituted with oxygen. Here, the methylene group contains -CH ₂ -, -CFH- or -CF ₂ -. That is, "arbitrary methylene group may be substituted by oxygen" means that -CH ₂ -, -CFH- or -CF ₂ - may be substituted by -O-. However, in the fluoroalkyl group, two oxygens are not bonded (-OO-). That is, the fluoroalkyl group may also have an ether bond. Further, in a preferred fluoroalkyl group, the methylene group adjacent to Si is not substituted by oxygen, and the terminal opposite to Si is CF ₃ . Further, it is preferred that -CF ₂ - is substituted with oxygen as compared with -CH ₂ - or -CFH- by oxygen substitution. Preferred specific examples of the fluoroalkyl group 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-tetrahydrododeyl, twenty-first fluorine- 1,1,2,2-tetrahydrododecyl, twenty-fivefluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy)propyl, and the like. Among them, a perfluoroalkylethyl group may be preferably exemplified, and a fluoroalkyl group may be bonded via -CH ₂ -CH ₂ -, or a fluoroalkyl group may be bonded via -CH ₂ - base.

The above fluoroarylalkyl group is an alkyl group containing a fluorine-containing aryl group, and its carbon number is higher. Good for 7~20, better for 7~10. It is preferred that the fluorine contained is one in which one or two or more hydrogens in the aryl group are substituted with fluorine or a trifluoromethyl group. Examples of the aryl moiety include a phenyl group, a naphthyl group, and a heteroaryl group. Examples of the alkyl moiety include a methyl group, an ethyl group, and a propyl group.

Further, the fluoroaryl group is one in which one or two or more hydrogens of the aryl group are substituted by fluorine or a trifluoromethyl group, and the carbon number thereof is preferably from 6 to 20, more preferably 6. Examples of the aryl group include a phenyl group, a naphthyl group, and a heteroaryl group. Specific examples thereof include a fluorophenyl group such as pentafluorophenyl group and a trifluoromethylphenyl group.

Among the above fluoroalkyl groups, fluoroarylalkyl groups or fluoroaryl groups contained in the fluorosesquioxane, a preferred group is a fluoroalkyl group, more preferably a perfluoroalkylethyl group, and thus more preferably Is 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl or tridecafluoro-1,1,2,2-tetrahydrooctyl .

As described above, a preferred fluorosesquioxane has a T8 type structure, has one addition polymerizable functional group, and has one or more fluoroalkyl groups, fluoroarylalkyl groups and/or Fluorinyl group and represented by the following structural formula (1).

[Chemistry 7]

In the above formula (1), A ¹ is an addition polymerizable functional group, preferably a radical polymerizable functional group, and R _f ¹ to R _f ⁷ are each independently a fluoroalkyl group or a fluoroaryl group. Alkyl, or fluoroaryl. R _f ¹ to R _f ⁷ may each be a different group or may be the same group.

R _f ¹ to R _f ⁷ in the formula (1) preferably independently represent 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3, respectively. 4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptafluoro-1,1,2,2-tetrahydroindole Base, hexafluoro-1,1,2,2-tetrahydrododecyl, twenty-five fluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) Propyl, pentafluorophenylpropyl, pentafluorophenyl, or α,α,α-trifluoromethylphenyl, R _f ¹ to R _f ^{7 more} preferably independently represent 3,3,3-three Fluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, or tridecafluoro-1,1,2,2-tetrahydrooctyl.

The compound (a-1) described in [Production Example 1] of International Publication No. WO 2008/072765 is exemplified as a specific compound.

[化8]

Next, the constituent unit B derived from sesquiterpene oxide having no fluorine-containing sesquioxane and having 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 the group consisting of the sesquiterpene oxide derivatives represented by the formulae (A-1) to (A-3).

[Chemistry 9]

In the formulae (A-1) to (A-3), R is independently hydrogen, and the non-contiguous -CH ₂ - may be an alkyl group having 1 to 45 carbon atoms which may be substituted by -O- or a cycloalkyl group. A cycloalkyl group having 4 to 8 carbon atoms or a substituted or unsubstituted aryl group. In the benzene ring of the substituted aryl group, any hydrogen may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen.

More preferably R is cyclopentyl, cyclohexyl, or any hydrogen may be chlorine, fluorine, Methyl, methoxy or trifluoromethyl substituted phenyl, more preferably R is cyclohexyl or phenyl, and most preferably R is phenyl.

R ^{1 is} each independently a group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, and a phenyl group. Examples of the alkyl group having 1 to 4 carbon atoms are a methyl group, an ethyl group, a propyl group, a 2-methylethyl group, a butyl group and a tert-butyl group. Preferred examples of R ¹ are a methyl group and a phenyl group. Preferably, R ¹ is the same group.

At least two of X are hydrogen or 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, it may, for example, be an ethylene oxide group, an ethylene oxide group, a 3,4-epoxycyclohexyl group, an oxetanyl group, an oxetanyl group, or a vinyl group. Any one of the allyl or styryl groups. In the present invention, it is preferred to have any one of an ethylene oxide group, an ethylene oxide group, a 3,4-epoxycyclohexyl group, an oxetanyl group and an oxetanyl group. Residues of each substituent.

[化10]

Next, a specific compound belonging to the constituent unit B is exemplified.

<Compound Example 1>

In the example of the Japanese Patent Publication No. 2009-167390, the compound (1) is represented by the following formula in [Synthesis Example 1].

[11]

<Compound Example 2>

In the example described in the Japanese Patent Publication No. 2007-326988, the compound (1-1) is represented by the following formula in [Synthesis Example 1].

<Compound Example 3>

The compound example 3 is described as the compound (b-1-1) in the first embodiment of JP-A-2010-254814, and is represented by the following formula.

[Chemistry 13]

Next, the polymerizable resin C will be described.

a fluorosilsesquioxane derivative constituting the unit A or a half of the constituent unit B The siloxane derivative can be used in combination with the polymerizable resin C. In the present invention, the "polymerizable resin C" is a general term for a polymerizable resin having a high molecular weight, a polymerizable oligomer having a weight average molecular weight of several hundreds to several thousands, and a polymerizable monomer.

If it is formed on the surface of the substrate by the resin composition of the present invention In the film, the polymerizable resin C having a crosslinking component is used in at least one selected from the group consisting of a fluorosilsesquioxane derivative of the structural unit A and a sesquioxane derivative of the structural unit B. Improve the heat resistance, light resistance, scratch resistance, abrasion resistance and surface of the cured film. Interface characteristics, compatibility and other characteristics.

Specifically, for example, by containing a sesquiterpene oxide having a polymerizable group The derivative and the polymerizable polyfunctional compound, and optionally a solution containing a polymerization initiator (hardening reaction), are applied onto the substrate, and the coating film is dried and hardened to form a film containing the composite resin on the substrate. (composite film).

The polymerizable resin C may be any of a thermoplastic resin and a thermosetting resin. It can also be a plurality of kinds of compounds.

As the polymerizable resin C, for example, polyethylene, polypropylene, and polychloride are included. Ethylene, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly(meth)acrylate resin, ultrahigh molecular weight polyethylene, poly-4-methyl Synetactic polystyrene, polyamine (for example, nylon 6: trade name of DuPont, nylon 6,6: trade name of DuPont, nylon 6,10: trade name of DuPont), Nylon 6, T: DuPont's trade name, nylon MXD6: DuPont's trade name, etc.), polyester (such as polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6- Naphthalene dicarboxylate), polyacetal, polycarbonate, polyphenylene ether, fluororesin (eg polytetrafluoroethylene, polyvinylidene fluoride), polyphenylene sulfide, polyfluorene, polyether oxime, polyether ether Ketones, polyarylates [eg U-polymer: the trade name of Unitika (shares), Vectra: the trade name of Polyplastics (shares)], polyimine [eg Kapton: East The trade name of Li (share), AURUM: the trade name of Mitsui Chemicals Co., Ltd., polyether oximine, polyamidimide, phenol resin, alkyd resin Melamine resins, epoxy resins, urea resins, bismaleimide resins (PEI), polyester urethane resins, polyether urethane silicone resin, ketone resin and the like. These resins may be used singly or in combination of a plurality of resins.

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

In the present invention, when an epoxy resin is used as the polymerizable resin C, an example is given. Examples thereof include bisphenol A, bisphenol F, bisphenol AD, bromine-containing bisphenol A, phenol novolac, cresol novolak, polyphenol, linear aliphatic, and dibutyl A glycidyl ether type epoxy resin such as an olefin or a urethane type; a glycidyl hexahydrophthalate, a glycidyl dimerate, an aromatic system, a cyclic aliphatic system, or an aliphatic system. Glyceryl ester type epoxy resin; bisphenol type, ester type, high molecular weight ether ester type, ether ester type, bromine type, novolak type, methyl substituted type epoxy resin; heterocyclic epoxy resin; triglycidyl group a glycidylamine type epoxy resin such as isomeric cyanurate or tetraglycidyldiamine diphenylmethane; a linear aliphatic epoxy resin such as epoxidized polybutadiene or epoxidized soybean oil; An aliphatic epoxy resin, a naphthalene novolak epoxy resin, or a diglycidoxy naphthalene epoxy resin. Among these, in terms of performance and economy, a bisphenol A type, a bisphenol F type, and a bisphenol AD type glycidyl ether type epoxy resin are particularly preferable.

In addition, within the scope of not impairing the performance of the present invention, it may also be to the ring as needed. Additives such as a flexible agent, a coupling agent, a flame retardant, a flame retardant auxiliary, a coloring agent, and a filler which are usually formulated in the field of use are further added to the oxygen resin.

When the hardened resin obtained by hardening the resin composition of the present invention is adjusted When the liquid epoxy resin is added, the fluidity of the resin in the semi-hardened state can be further improved, and when the sheet is formed into a sheet shape, the sheet is hard to be broken, and it is easy to cut, etc., and the handleability can be improved, so that the liquid epoxy resin is obtained. Can also be used as a diluent.

The liquid epoxy resin is not particularly limited as long as it is in a liquid form. For the polyfunctional liquid epoxy resin, for example, Epikote E152 [product name, Liquid epoxy phenol novolak type epoxy resin such as Japan Epoxy Resins (manufactured by Japan Epoxy Resins), Epiclon N730-S [trade name, manufactured by Dainippon Ink (product)], Epikote E827, Epikote E828 [both Liquid bisphenol A type epoxy resin such as product name, Japanese epoxy resin (manufactured by Japan), liquid bisphenol A, etc., Epikote E806, Epikote E807 [all trade names, manufactured by Japan Epoxy Co., Ltd.] Type epoxy resin, Epikote E630 [trade name, manufactured by Japan Epoxy Resin Co., Ltd.], liquid Glycidylamine type epoxy resin such as GOT, GAN [trade name, manufactured by Nippon Chemical Co., Ltd.], EPU-73 [product name, Asahi Chemical Industry Co., Ltd.] and other liquid urethane modified bisphenol A type epoxy resin, YED122, YED111N [all trade names, manufactured by Japan Epoxy Co., Ltd.] Liquid epoxy resin such as epoxy resin.

The lower limit of the epoxy value (also known as epoxy equivalent) of the above epoxy resin is Preferably, it is 150 or more, more preferably 170 or more, and most preferably 190 or more. Further, the upper limit of the epoxy value of the epoxy resin is preferably 700 or less, more preferably 500 or less, and most preferably 300 or less.

If the epoxy resin of the above epoxy resin is less than 150, the resin of the present invention is used. Since the polar group in the hardened resin obtained by hardening the composition increases, dielectric properties may be impaired. That is, the dielectric constant or the dielectric loss tangent of the cured resin may become high. On the other hand, when the epoxy value exceeds 700, the crosslinking density in the cured resin is lowered, and thus heat resistance may be impaired.

Further, in order to increase the crosslinking density in the cured resin, it is preferred to use more A functional epoxide compound is used as the polymerizable resin C. Multi-official that can be used in the present invention The energy epoxide 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 use and purpose. Among these, a preferred compound is one having 2 to 6 epoxy groups in the molecule. Hereinafter, the polyfunctional epoxide compound (monomer) is classified by structure to be exemplified.

(EP-1) Diglycidyl ether of dihydric phenols

Examples of the diglycidyl ether of the dihydric phenols include diglycidyl ethers of dihydric phenols (C6 to C30). Examples of the diglycidyl ether of the dihydric phenol (C6 to C30) include 2 mol of bisphenol F diglycidyl ether, bisphenol-A diglycidyl ether, and bisphenol-B diglycidyl ether. Bisphenol-AD diglycidyl ether, bisphenol-S diglycidyl ether, halogenated bisphenol A diglycidyl ether (tetrachlorobisphenol A diglycidyl ether, etc.), catechin diglycidyl ether, isophthalic acid Phenol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl condensed water Diffused water obtained by the reaction of glyceryl ether, tetramethylbiphenyl diglycidyl ether, 9,9'-bis(4-hydroxyphenyl)indole diglycidyl ether, bisphenol A and 3 mol of epichlorohydrin Glycerol ether.

(EP-2) Polyglycidyl ether of ternary or higher polyphenols

Examples of the polyglycidyl ether of a trihydric or higher polyhydric phenol include gallic phenol triglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, and dinaphthyl. Triol triglycidyl ether, tetrakis(4-hydroxyphenyl)ethane tetraglycidyl ether, p-glycidyl phenyl dimethyl triol bisphenol A glycidyl ether, trimethyl-tert-butyl- Butyl hydroxymethane triglycidyl ether, 4,4'-oxybis(1,4-phenylethyl)tetramethyl phenol glycidyl ether, 4,4'-oxybis (1,4-phenylene) Phenyl Glycidyl ether, bis(dihydroxynaphthalene) tetraglycidyl ether, phenol novolac resin or cresol novolac resin (Mn 400~5,000) glycidyl ether, limonene phenol novolac resin (Mn 400~5,000) Glycidyl ether, polyglycidyl ether of polyphenol (Mn 400-5,000) obtained by condensation reaction of phenol with glyoxal, glutaraldehyde or formaldehyde, and condensation of resorcinol with acetone The polyglycidyl ether of polyphenol having a Mn of 400 to 5,000 obtained by the reaction.

(EP-3) diglycidyl ether of aliphatic diol

Examples of the diglycidyl ether of the aliphatic diol include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, and 1,6-hexanediol condensed water. Glycerol ether, polyethylene glycol (Mn 150-4,000) diglycidyl ether, polypropylene glycol (Mn 180-5,000) diglycidyl ether, polytetramethylene glycol (Mn 200-5,000) diglycidyl Ethylene ether, neopentyl glycol diglycidyl ether, bisphenol A alkylene oxide [Ethylene Oxide (EO) or propylene oxide (Propylene Oxide, PO) (1 mol ~ 20 mol)] The diglycidyl ether of the adduct.

(EP-4) Polyglycidyl ether of ternary or higher aliphatic alcohol

Examples of the polyglycidyl ether of a trivalent or higher aliphatic alcohol include trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexa glycidyl ether, and poly(n). = 2~5) Glycerol polyglycidyl ether.

(EP-5) glycidyl ester type

Examples of the glycidyl ester of the (i) aromatic polycarboxylic acid include glycidyl esters of phthalic acid. As a glycidyl ester of phthalic acid, for example Listed: diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, triglycidyl trimellitate.

Examples of the glycidyl ester of the aliphatic polycarboxylic acid or the alicyclic polycarboxylic acid (ii) include an aromatic nuclear hydrogenated product of the above phenolic glycidyl ester, dimerized acid diglycidyl ester, and oxalic acid dihydrate. Glyceryl ester, diglycidyl maleate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, (meth)acrylic acid The (co)polymer of glycidyl ester (degree of polymerization is, for example, 2 to 10), and triglycidyl 1,2,3-propane tricarboxylate.

(EP-6) glycidylamine type

Examples of the (i) aromatic amine-based glycidylamine include N,N-diglycidylaniline, N,N-diglycidyltoluidine, N,N,N',N'-tetrahydration. Glyceryldiaminodiphenylmethane, N,N,N',N'-tetraglycidyldiaminodiphenylphosphonium, N,N,N',N'-tetraglycidyldiethyl Phenylmethane, N, N, O-triglycidylaminophenol.

Examples of the glycidylamine of (ii) an aliphatic amine include N, N, N', N'-tetraglycidylbenzenediamine, N, N, N', N'-tetraglycidyl. Hexamethylenediamine.

Examples of the (iii) glycidylamine-derived glycidylamine include a hydrogenated compound of N,N,N',N'-tetraglycidylbenzenediamine.

Examples of the glycidylamine of the (iv) heterocyclic amine include triglycidyl melamine.

(EP-7) chain aliphatic epoxide

Examples of the chain aliphatic epoxide include an epoxy equivalent of 130~. 1,000 epoxidized polybutadiene (Mn is 90~2,500) and epoxidized soybean oil (Mn is 130~2,500).

(EP-8) alicyclic epoxide

Examples of the alicyclic epoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl) ether, and B. Glycol bis(epoxy)dicyclopentyl ether, 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. Further, a nuclear hydrogenated product of the above phenolic epoxy compound is also included.

Further, these polyepoxy compounds may be used in combination of two or more kinds. Among these, Preferred are glycidyl ether type and glycidyl ester type.

Examples of the oxetane compound include C6 to C20 fat. a family of oxetane compounds (eg 3-ethyl-3-hydroxymethyl oxetane), C7-C30 aromatic oxetane compounds (eg benzyl oxetane and Benzene dimethyl dioxetane), C6-C30 aliphatic carboxylic acid oxetane compound (for example, adipate dioxetane), C8-C30 aromatic carboxylic acid system An oxetane compound (for example, terephthalate dioxetane), a C8 to C30 alicyclic carboxylic acid oxetane compound (for example, a cyclohexanedicarboxylic acid dioxyheterocycle) Butane, 3,3'-[methylenebis(oxymethylene)]bis(7-oxabicyclo[4.1.0]heptane and 3,3'-[ethylenebis(oxy) Methyl)]bis(7-oxabicyclo[4.1.0]heptane), aromatic isocyanate oxetane compound (for example, Methylene Diphenyl Diisocyanate, MDI) Cyclobutane), C2~ a sulfur-based oxetane compound of C20 (e.g., ethylene sulfide, 2-methylcycloethane, 2,2-dimethylcycloethane, 2-hexylcycloethane, and 2-phenyl) Ethylene sulfide).

Further, examples of the polymerizable resin C include polyfunctional acrylic acid. A monomer or oligomer.

Examples of the compound of the difunctional acrylic monomer include 1,3- Butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(methyl) Acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxyl Trimethyl acetate neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, bis[(meth)acryloxyethoxyethoxy]bisphenol A, double [(Meth)acryloxyethoxyethoxy]tetrabromobisphenol A, bis[(meth)acryloxypolyethoxy]bisphenol A, 1,3-bis(hydroxyethyl)5, Bis(methyl) acrylate of 5-dimethylhydantoin, 3-methylpentanediol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol compound, double [(A) A di(meth)acrylate monomer such as acryloxypropyl]tetramethyldioxane and divinylbenzene.

Further, for example, (poly)oxyethylene (preferably, polymerization degree = 4~) 20) di(meth)acrylate, (poly)oxypropylene (preferably degree of polymerization = 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 degree of polymerization = 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 degree of polymerization = 4-6) hydrogenated bisphenol A. Di(meth)acrylate.

Examples of the compound of the trifunctional acrylic monomer include, for example, three. Hydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, tris(2-hydroxyethyl isocyanate) Tris(meth)acrylate, tris(diethylene glycol)tri(meth)acrylate, 3,7,14-tris[(((methyl)propenyloxypropyl)dimethyl decyloxy) Base]]-1,3,5,7,9,11,14-heptyltricyclo[7.3.3.15.11] heptaoxane, 3,7,14-tri[(((meth)propene)醯oxypropyl) dimethyl decyloxy)]-1,3,5,7,9,11,14-heptylbutyltricyclo[7.3.3.15.11] heptaoxane, 3,7 , 14-tris[(((methyl) propyleneoxypropyl) dimethyl decyloxy)]-1,3,5,7,9,11,14-heptyloctyltricyclo[7.3. 3.15.11] heptaoxane, 3,7,14-tri[(((methyl)propenyloxypropyl)dimethylamoxy)]-1,3,5,7,9,11 , 14-heptacyclopentyltricyclo[7.3.3.15.11] heptaoxane and 3,7,14-tri[(((methyl)propenyloxypropyl)dimethylamyloxy)]] -1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.15.11] heptaoxane.

Further, for example, glycidyl methacrylate or methacrylic acid may be mentioned. Acid 2-methyl-glycidyl ester, epoxidized isoamyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, ethyl 2-(hydroxymethyl)acrylate, 1-allyl -2,3-epoxypropane, 2-propenylamine-2-methylpropanesulfonic acid, N,N'-dipropenyl-1,2-dihydroxyethylenediamine, 2-hydroxyethyl acrylate a monomer of N,N'-methylenebispropenylamine or N-propylenenonoxysuccinimide.

A hardening accelerator and ultraviolet light absorber may be added to the resin composition of the present invention. The following ingredients can also be formulated with a receiving agent or an antioxidant.

(1) A powdery reinforcing agent or filler. For example, high refractive index metal oxides such as zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), nano cerium oxide (SiO ₂ ), and zinc oxide (ZnO ₂ ) may be mentioned. Metal oxides, fine powders such as cerium oxide, molten cerium oxide and crystalline cerium oxide, transparent fillers such as glass beads, metal hydroxides such as aluminum hydroxide, kaolin, mica, quartz powder, graphite and disulfide molybdenum. In particular, by adding nano cerium oxide, the absolute amount of the SiO ₂ component after the surface treatment can be increased and changed to a more hydrophilic surface. These components are blended in a range that does not impair the transparency of the resin composition of the present invention. A preferred ratio when the components are blended with respect to the mass ratio of the total amount of the resin composition of the present invention is in the range of 0.10 to 1.0.

(2) A colorant or pigment. For example, titanium dioxide, molybdenum red, Iron blue, ultramarine blue, cadmium yellow, cadmium red and organic pigments.

(3) Flame retardant. For example, antimony trioxide, a bromine compound, and a phosphorus compound are mentioned.

(4) Ion absorbing body.

A preferred ratio when the components are blended in a mass ratio with respect to the total amount of the resin composition is 0.0001 to 0.30.

(5) A decane coupling agent containing no epoxy group or oxetanyl group in the molecule.

(6) A nanoparticle dispersion of a metal oxide such as zirconium oxide, titanium oxide, aluminum oxide or cerium oxide.

A preferred ratio when the components of the above (1) to (6) are blended in a mass ratio with respect to the total amount of the resin composition is 0.01 to 0.50.

The resin composition of the present invention comprises a component selected from the constituent unit A and a constituent sheet At least one of the element B and the polymerizable resin C, the structural unit A is derived from a fluorosilsesquioxane having an addition polymerizable functional group in the molecule, and the constituent unit B is derived from a fluorine-free sesquioxide The alkane and a sesquioxane having a plurality of polymerizable functional groups in the molecule, and the resin may have a structure of a block copolymer or a random copolymer, but must have a crosslinked structure.

The constituent unit A and the constituent unit B in the resin composition of the present invention The mass ratio of the conjugate resin C is preferably in the range of (A): (B) = 0: 100 to 100: 0, (B): (C) = 5: 95 to 99: 1. When a plurality of monomer compounds are used, the ratio of each monomer may be appropriately determined in accordance with the characteristics of the intended resin composition. On the other hand, in order to make the resin composition into a film shape and to hydrophilize the surface in a short time, it is preferred to form a constituent unit A and/or a composition containing sesquiterpene oxide with respect to the entire mass of the resin composition. The mass ratio of the unit B is maintained in the range of preferably from 10 parts to 80 parts, more preferably from 20 parts 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 form a cured film having a hydrophilized surface, it is preferred to select a polyfunctional epoxide or a hydrophilic polyfunctionality. The acrylic compound is used as a copolymerization component of the resin composition.

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

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

If an epoxy resin containing no ruthenium atoms in the molecule is used, or ruthenium is not contained in the molecule The oxetane resin is preferred as a diluent because it is hardened together with the organic hydrazine compound of the present invention by a curing agent.

Specific examples of the epoxy resin containing no ruthenium atom in the molecule may be listed Acetone: epoxide-A type, bisphenol-F type, bisphenol-S type, hydrogenated bisphenol-A type epoxy resin, Celloxide (trade name) manufactured by Daicel Chemical Industry Co., Ltd. ) 2021P, Celloxide (trade name) 3000, Celloxide (trade name) 2081 and other alicyclic epoxy resins.

Further, as a specific example of the oxetane resin containing no antimony in the molecule, An oxetane resin such as ARONE OXETANE (registered trademark) manufactured by Toagosei Co., Ltd. can be cited. Further, a decane coupling agent containing an epoxy group or an oxetanyl group in the molecule may be mentioned. Specific examples of the decane coupling agent include a decane coupling agent such as SILA-ACE (trade name) S510, S520, and S530 manufactured by JC (product).

The weight average molecular weight of the resin composition of the present invention is based on the constitution The content rate of the unit C is different, but it is 1,000 to 1,000,000. On the other hand, the polymer of the present invention has a molecular weight distribution (Mw/Mn) of about 1.01 to 2.5.

The preparation method of the resin composition is based on the constituent unit A~ constituent unit The type of B differs from the ratio of the constituent units and the characteristics of the intended resin composition. However, in view of simplicity and versatility, it is preferred to employ radical polymerization or cationic polymerization in a part of the curing step. In addition, there are no problems in the use of radical polymerization and cationic polymerization in stages. In the present invention, it is preferred to harden the step A cationic polymerization initiator is used in the initial stage of the step.

As a cationic polymerization initiator, for example, an active energy ray is exemplified An active energy ray cationic polymerization initiator which produces a cationic species or a Lewis acid, and a thermal cationic polymerization initiator which generates a cationic species or a Lewis acid by heat.

As the active energy cation polymerization initiator, for example, a metal is exemplified Fluoroboron salt and boron trifluoride complex (U.S. Patent No. 3,375,653), bis(perfluoroalkylsulfonyl)methane metal salt (US Patent No. 3,586,616), aryldiazo compound (USA) Patent No. 3,708,296), aromatic sulfonium salt of Group VIa (U.S. Patent No. 4058400), aromatic sulfonium salt of Group Va element (U.S. Patent No. 4,609,905), Group IIIa to Va a carbonyl chelate (U.S. Patent No. 4,406,091), a thiopyranium salt (U.S. Patent No. 4,139,655), a group VIb element of the form of MF6-anion (U.S. Patent No. 4,161,478; M from phosphorus, cesium) And arsenic selected), aryl sulfonium salt (US Patent No. 4231951), aromatic sulfonium salts and aromatic sulfonium salts (US Patent No. 4256828), and bis[4-(diphenyl fluorene) Phenyl]sulfide-bis-hexafluorometal salt [Journal of Polymer Science, Polymer Chemistry, Vol. 2, item 1789 (1984)]. Further, for example, a mixed ligand metal salt of an iron compound and a stanol-aluminum complex are mentioned.

An example of a preferred active energy cation polymerization initiator is aryl hydrazine. A salt, an aromatic sulfonium salt or an aromatic sulfonium salt containing a halogen ion, and an aromatic sulfonium salt of a Group II element, a Group V element, and a Group VI element. Several of these salts can be used as Obtained from the goods.

As the thermal cationic polymerization initiator, for example, a cationic catalyst such as trifluoromethanesulfonic acid salt or boron trifluoride or a protonic acid catalyst can be used. As a preferable thermal cationic polymerization initiator, a trifluoromethanesulfonate is mentioned, for example.

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

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

Among these cationic polymerization initiators, an aromatic sulfonium salt is preferred in terms of excellent balance between handleability and potential and curability, and in terms of excellent balance between handleability and potential Preferred are diazonium salts, phosphonium salts, phosphonium salts and phosphonium salts. The cationic polymerization initiators may be used singly or in combination of two or more.

The preferred ratio of use of the cationic polymerization initiator is 0.0005 to 0.05, based on the total mass ratio of the epoxy resin used.

When the resin composition of the present invention containing at least one of the structural unit A and the constituent unit B and the polymerizable resin C is produced from a radical polymerizable monomer, a radical polymerization initiator can be used. .

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-couple. An azo compound such as nitrogen bis(2-butyronitrile), dimethyl-2,2'-azobisisobutyrate or 1,1'-azobis(cyclohexane-1-carbonitrile); benzene Formyl peroxide, lauryl peroxide, octyl peroxide, acetyl peroxy , di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, neodymium peroxide a peroxide such as a third butyl ester; and a dithiocarbamate such as tetraethylthiuram disulfide.

Further, examples of the polymerization reaction include living radical polymerization, And active energy ray polymerization.

In the present invention, the term "active energy ray" means that the active species can be produced. The compound decomposes to produce an energy line of the active species. Examples of such an active energy ray include light energy rays such as visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, gamma rays, and electron beams.

Specific examples of the active energy ray polymerization initiator are as long as they are ultraviolet The compound which generates a radical by irradiation of a line or visible light is not specifically limited. Examples of the compound usable as the active energy ray polymerization initiator include diphenyl ketone, rice ketone, 4,4′-bis(diethylamino)benzophenone, xanthone, Xanthone and isopropyl xanthone.

Film comprising the resin composition of the present invention, and a molded body having the film The step of forming a film from the resin composition of the present invention on the substrate, the step of hardening the film, and the step of surface-treating the film can be obtained by the following steps. The formation of the film can be carried out, for example, by coating, and the curing of the film can be usually carried out by one or two or more kinds of drying, heating, and active energy ray irradiation.

Applying a solution containing the resin composition of the present invention to a substrate The method is not particularly limited, and examples thereof include spin coating, roll coating, and slit coating. Method, dipping method, spray coating method, gravure coating method, reverse coating method, rod coating method, bar coating method, die coating method, contact coating method, reverse contact coating method, air knife coating method and curtain Coating method.

Examples of the substrate to be coated include white glass and blue glass. Transparent glass substrate such as cyanide glass coated with cerium oxide; polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamidimide, polyimine, triethyl A synthetic resin sheet or film such as an acid ester or a diacetate; or a cycloolefin resin containing a norbornene-based resin (for example, trade name: Zeonor, Zeonex, Japan Zeon Co., Ltd., trade name) : Arton, manufactured by JSR Co., Ltd.), transparent resin substrate for optical applications such as styrene methacrylate, polystyrene, alicyclic acrylic resin or polyarylate; metal substrate such as aluminum plate, copper plate, nickel plate or stainless steel plate Other ceramic plates, semiconductor substrates with photoelectric conversion elements; urethane rubber, styrene rubber.

The substrates may also be pretreated, and as a pretreatment, for example, Chemical treatment such as decane coupling agent, sandblasting treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, gas phase reaction, and vacuum evaporation. The drying of the applied solution can be carried out at room temperature to about 200 °C.

When the active energy ray polymerization initiator is used, after the coating is dried, it can be borrowed The active energy ray energy initiator or electron beam is irradiated by an active energy ray source to harden the active energy ray polymerization initiator.

As an active energy ray source, corresponding to the active energy ray polymerization used The properties of the initiator are, for example, low pressure mercury lamps, high pressure mercury lamps, and ultra high pressure water. Silver lamps, metal halide lamps, carbon arcs, xenon arcs, gas lasers, solid state lasers, and electron beam irradiation devices.

Then, the surface of the coated shaped body substrate is irradiated with a high energy line, whereby The shaped body is subjected to surface treatment. As the surface treatment, at least one selected from the group consisting of ozone treatment and ultraviolet irradiation treatment is preferred. As the ultraviolet irradiation treatment, deep ultraviolet (UV) irradiation with high energy is preferred, and a low-pressure mercury lamp that emits light at 185 nm and 254 nm and a krypton excimer lamp that emits light at 172 nm are generally used as the light source.

When the energy of the irradiated UV light is higher than the molecular bonding energy of the organic compound At the time of the measurement, the probability of the molecular bond being broken is high, but deep ultraviolet rays having a wavelength of 240 nm or less decompose the oxygen, so that 172 nm radiation and 185 nm radiation generate ozone from oxygen.

254nm deep ultraviolet light decomposes ozone to generate high energy activity oxygen. If 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. That is, the oxygen radical has a polarity, which increases the surface energy to enhance the hydrophilicity, thereby enhancing the adhesion force depending on the hydrophilicity.

The resin composition containing the sesquiterpene oxide derivative of the present invention will be halved A part of the siloxane structure is cerium oxide. Examples of the high energy ray used herein include an electron beam, ultraviolet rays, X-rays, infrared rays, and microwaves. Among these, ultraviolet rays are preferable, and in general, deep ultraviolet rays which are ultraviolet rays having a wavelength in the wavelength range of 200 nm to 350 nm generate ozone, which is more preferable.

High-energy line irradiation is preferably carried out in air or a gas containing oxygen. Row. Examples of the gas other than oxygen include nitrogen gas and argon gas. The temperature at the time of irradiation of the high-energy ray and the conversion temperature to cerium oxide are preferably such a temperature as possible to suppress the scattering of the low molecular weight sesquiterpene-based resin, and it is preferably in the range of 10 ° C to 50 ° C.

In order to obtain a cured product having a hydrophilized surface, various materials can be selected as described above, and various steps are employed. However, in the present invention, it is preferred to produce a cured product by the following procedure.

(1) comprising a constituent unit A selected from a fluorosilsesquioxane having an addition polymerizable functional group and/or derived from a fluorine-free sesquioxane, and having a plurality of polymerizable functional groups in the molecule At least one of the constituent units B of the sesquiterpene oxide of the group is stirred and mixed with the resin composition of the polymerizable resin C (for example, a polyfunctional monomer), and further a cationic polymerization initiator is added and preferably used in the chamber. Mix and dissolve at a temperature of ~50 °C.

(2) After mixing and dissolving, decompression is carried out to defoam. Then, the mixture is spin-coated on a substrate such as glass, and then (a) a thermal cationic hardener (cationic polymerization initiator) is added as a hardener, preferably at 80 ° C to 100 ° C, preferably for 5 minutes. 20 minutes, and finally preferably at 120 ° C to 160 ° C, preferably for 30 minutes to 60 minutes for hardening; or (b) addition of photocationic hardener (cationic polymerization initiator), preferably 50 mJ Ultraviolet rays (i-rays) of /cm ² to 2000 mJ/cm ² are preferably exposed to light for 0.1 minute to 60 minutes.

(3) Further, the cured product to be produced is subjected to a surface treatment by irradiating deep ultraviolet rays, whereby a cured product having a hydrophilic surface can be obtained.

As a result, it is possible to obtain a cured product having a contact angle of water of less than 10°, especially if With respect to the overall mass of the resin composition, the mass ratio of the constituent unit A and/or the constituent unit B containing sesquiterpene oxide is preferably from 10 parts to 80 parts, more preferably from 20 parts to 80 parts, and thus A cured product of a super-hydrophilic surface having a contact angle of 0.1 to 5°.

It is possible to obtain the above surface by using the resin composition of the present invention A cured surface of a functional surface obtained by treatment. As the functional surface, a superhydrophilic surface, a gas barrier layer, a hard coat layer or a heat resistant surface can be cited.

The super-hydrophilic surface refers to a surface having a contact angle of water of less than 10°. The so-called gas barrier layer means that the water vapor transmission rate is 10 ^-2 g/m ² . Layers below 24hr. The hard coat layer refers to a layer having a hardness of H or more in a pencil hardness test measured in accordance with JIS K 5600-5-4 (1999). The heat-resistant surface refers to a surface which can achieve a thermal property of a film or a composition by a glass transfer thermometer of 200 ° C or more and a linear expansion coefficient of 50 ppm / K or less.

Coating flattening property of the cured product of the present invention as described above In addition, it is excellent in embedding property of a step of a substrate having an electronic component having a package structure, and is a ruthenium dioxide film having excellent electrical insulating properties after being irradiated with a high-energy ray. Therefore, for example, a multilayer semiconductor is required for such characteristics. The interlayer insulating film and electronic material of the element are particularly useful.

[Examples]

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

(Example 1)

The sesquioxane derivative B described in [Synthesis Example 1] of JP-A-2009-167390 is described as "(1-1)" 1.8 g as a screw bottle (Screw Vial). a mixture of 7.3 g of an epoxy resin [Celloxide CEL2021P (trade name: Daicel) (share)) and 0.9 g of 2,2-bis(4-glycidoxyphenyl)propane (Tokyo Chemicals) of the polymerizable resin C, Heat and stir at 70 ° C. After dissolving for 20 minutes, 50 mg of a thermal cationic polymerization initiator San-Aid SI-100 was added as a hardener and dissolved. Set the screw bottle to the rotation. Mixing is carried out in a revolving mixer [Decoction Rantaro ARE-250 (trade name) manufactured by Thinky Co., Ltd.]. Defoaming is carried out to form a resin composition. The composition of the resin composition is shown in Table 1.

. [San-Aid SI-100 (trade name: manufactured by Sanshin Chemical Industry Co., Ltd.)] (aromatic cation type cationic polymerization initiator)

. [Celloxide CEL2021P (trade name: Daicel Industries)] (3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate)

Then, the bubble was applied to a glass substrate (40 mm × 40 mm) by a spin coater (500 rpm, 30 seconds) to a thickness of 150 μm, and heated at 100 ° C for 20 minutes. Then, it was heated at 150 ° C for 30 minutes to obtain a cured product.

The surface of the obtained cured product was irradiated with deep ultraviolet rays at a distance of 10 mm using a light surface treatment machine (PHOTO SURFACE PROCESSOR) [PL2003N-12 manufactured by SEN LIGHTS Co., Ltd.) (wavelength: 185 nm / 254 nm) The illuminance was 14.6 mW/cm ² ) for 0 minutes, 1 minute, 2 minutes, 5 minutes, and 10 minutes, and the respective water contact angles were measured. The water contact angle was measured by using a contact angle measuring device (DropMaster DM500, manufactured by Kyowa Interface Science Co., Ltd.), and after adding 1.8 μL of water droplets to the surface of the cured resin film, the position of the water was changed to determine the water contact angle at five points. average value. Further, in order to suppress the influence caused by the temporal change of the surface state, the contact angle measurement was performed on the day of deep ultraviolet irradiation. The results are shown in Table 2.

(Comparative Example 1)

A mixture of polymerizable resin C (Celloxide CEL2021P: 8.9 g, 2,2-bis(4-glycidoxyphenyl)propane: 1.1 g) was added and heated and stirred. After dissolution, 50 mg of a thermal cationic polymerization initiator (San-Aid SI-100) was added as a hardener and dissolved. Set the screw bottle to the rotation. Mixing is carried out in a revolution mixer [Decoction Rantaro ARE-250 (trade name) manufactured by Shinki Co., Ltd.]. Defoaming is carried out to form a resin composition. The composition of the resin composition is shown in Table 1.

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

According to the results shown in Table 2, by irradiating deep ultraviolet rays, the present invention The cured product of Example 1 containing the sesquioxane derivative B (1-1) was hydrophilic in comparison with the cured product of Comparative Example 1 containing no sesquioxane derivative B (1-1). This point shows obvious superiority in a short time.

Therefore, it can be seen that when a hard coat film is produced, it is initiated by cationic polymerization. Or a radical polymerization initiator to pre-harden the resin composition by heating, and then cross-link harden by heat or irradiation of energy rays at a higher temperature, and finally irradiate the deep ultraviolet rays to perform surface treatment. This makes it possible to obtain a functional film having an enhanced film strength and having a super-hydrophilic surface in a short time.

Although the invention has been described in detail using specific embodiments, It is apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. In addition, this application is based on a Japanese patent application filed on Jan. 25, 2013 (Japanese Patent Application No. 2013-012113) And quote all of its contents.

[Industrial availability]

The cured product obtained by subjecting the resin composition of the present invention to surface treatment is excellent in hydrophilicity, thermal stability, physical strength, uniformity, surface characteristics, and the like, and is expected to be used in a gas barrier film or an electronic material.

Claims (22)

A cured product having a functional surface obtained by subjecting a resin composition to a surface treatment, the resin composition comprising a monomer compound providing at least one constituent unit selected from the group consisting of the constituent unit A and the constituent unit B, and polymerization The resin C, the above-mentioned structural unit A is derived from a fluorosilsesquioxane having an addition polymerizable functional group in the molecule, and the above-mentioned constituent unit B is derived from a fluorine-free sesquioxane and has a plurality of polymerizable groups in the molecule. A functional sesquioxane. The cured product according to claim 1, wherein the above-mentioned fluorosilsesquioxane having an addition polymerizable functional group is represented by the following formula (1): In the formula (1), R _f ¹ to R _f ⁷ each independently represent an arbitrary methylene group which may be substituted by oxygen with a fluoroalkyl group having 1 to 20 carbon atoms and at least one hydrogen substituted by fluorine or trifluoromethyl group. a fluoroaryl group having 6 to 20 carbon atoms or at least one hydrogen in the aryl group substituted with fluorine or a trifluoromethyl group having 7 to 20 carbon atoms, and A ¹ representing an addition polymerization functional group base. The cured product according to claim 2, wherein R _f ¹ to R _f ⁷ in the above formula (1) independently represent 3,3,3-trifluoropropyl, 3,3,4,4 , 5,5,6,6,6-nonafluorohexyl, or tridecafluoro-1,1,2,2-tetrahydrooctyl. The cured product according to claim 2, wherein A ¹ in the above formula (1) is a radical polymerizable functional group. The cured product according to claim 4, wherein A ¹ in the above formula (1) contains a (meth)acrylic group or a styryl group. The cured product according to claim 5, wherein A ¹ in the above formula (1) is represented by the following formula (3) or formula (5): In the above formula (3), Y ¹ represents an alkylene group having 2 to 10 carbon atoms, R ⁶ is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and the above formula ( In 5), Y ² represents a single bond or an alkylene group having a carbon number of 1 to 10. The hardened material according to claim 6, wherein in the above formula (3), Y ¹ represents an alkylene group having a carbon number of 2 to 6, and R ⁶ represents hydrogen or a methyl group, and in the above formula (5), Y ² represents a single bond or an alkylene group having a carbon number of 1 or 2. The cured product according to the first aspect of the invention, wherein the structural unit B derived from a sesquioxane having no fluorine-containing sesquioxane and having a plurality of polymerizable functional groups in the molecule contains the following formula (A-1)~ at least one sesquiterpene derivative represented by the formula (A-3): In the formulae (A-1) to (A-3), R is independently hydrogen, and the non-adjacent -CH ₂ - may be an alkyl group having 1 to 45 carbon atoms which may be substituted by -O- or a cycloalkyl group. a cycloalkyl group having 4 to 8 carbon atoms or a substituted or unsubstituted aryl group; in the benzene ring of the substituted aryl group, any hydrogen may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen; ^{1 is} independently a group selected from an alkyl group having a carbon number of 1 to 4, a cyclopentyl group, a cyclohexyl group, and a phenyl group; at least one group having a hydrogen atom or a polymerizable functional group, and the remaining X is A group defined in the same manner as R ¹ . The cured product according to claim 8, wherein in the above formula (A-1) to formula (A-3), R is a phenyl group or a cyclohexyl group. The cured product according to claim 8, wherein the X is a group represented by any one of the formula (2), the formula (3), the formula (4), and the formula (5): The hardened material according to claim 8, wherein the above-mentioned constituent unit B derived from sesquioxane having no fluorine-containing sesquioxane and having a plurality of polymerizable functional groups in the molecule is represented by the following formula The sesquioxane derivative represented by (1-1): The cured product according to the first aspect of the invention, wherein the polymerizable resin C is at least one selected from the group consisting of a thermoplastic resin, a thermosetting resin, and/or an active energy ray-curable resin. The cured product according to claim 1, wherein the polymerizable resin C is selected from the group consisting of a (meth) acrylate resin, a polyurethane resin, a biodegradable resin, a polyvinyl alcohol resin, and an acrylamide. At least one or more of a urethane resin, a polyolefin resin, an epoxy resin containing no antimony in the molecule, and an oxetane resin containing no antimony in the molecule. The cured product according to claim 1, wherein the surface treatment is ozone treatment and/or ultraviolet irradiation treatment. The cured product according to claim 1, wherein the functional surface imparted by the surface treatment is a superhydrophilic surface. The cured product according to claim 1, wherein the functional surface imparted by the surface treatment is a gas barrier layer. The cured product according to claim 1, wherein the functional surface imparted by the surface treatment is a hard coat layer. The cured product according to claim 1, wherein the functional surface imparted by the surface treatment is a heat resistant surface. A film produced from a resin composition containing a monomer compound which provides at least one constituent unit selected from the constituent unit A and the constituent unit B, and a polymerizable resin C, wherein the constituent unit A is derived from a molecule A fluorosilsesquioxane having an addition polymerizable functional group therein, and the above-mentioned structural unit B is derived from a sesquioxane having no fluorine-containing sesquioxane and having a plurality of polymerizable functional groups in the molecule. A resin composition comprising a monomer compound which provides at least one constituent unit selected from the group consisting of a constituent unit A and a constituent unit B, and a polymerizable resin C, wherein the constituent unit A is derived from a molecule a fluorosilsesquioxane having an addition polymerizable functional group, wherein the above-mentioned constituent unit B is derived from a sesquioxane having no fluorinated sesquioxane and having a plurality of polymerizable functional groups in the molecule, and the above resin The contact angle of the (film) surface of the composition subjected to hardening and surface treatment is less than 10°. A coating film produced from a resin composition containing a monomer compound which provides at least one constituent unit selected from the constituent unit A and the constituent unit B, and a polymerizable resin C, the constituent unit A source The fluorosilsesquioxane having one addition polymerizable functional group in the molecule, and the above-mentioned structural unit B is derived from a sesquioxane having no fluorine-containing sesquioxane and having a plurality of polymerizable functional groups in the molecule. A molded article produced from a resin composition comprising a monomer compound which provides at least one constituent unit selected from the constituent unit A and the constituent unit B, and a polymerizable resin C, wherein the constituent unit A is derived One inside the molecule The fluorosilsesquioxane to which a polymerizable functional group is added, and the above-mentioned structural unit B is derived from a sesquioxane having no fluorinated sesquioxane and having a plurality of polymerizable functional groups in the molecule.