JP5920590B2 - Fluorine-containing highly branched polymer and photocationic polymerizable composition containing the same - Google Patents

Description

  The present invention relates to a fluorine-containing highly branched polymer containing a photocationically polymerizable group, a photocationically polymerizable composition to which the highly branched polymer is added, and a surface-modified cured product obtained from the photocationically polymerizable composition.

  In recent years, polymer materials have been increasingly used in many fields. Accordingly, the characteristics of the surface and interface of the polymer as a matrix are important as well as the properties of the polymer according to each field. For example, by using a fluorine-based compound with low surface energy as a surface modifier, water and oil repellency, antifouling properties, non-adhesiveness, peelability, release properties, slipperiness, abrasion resistance, antireflection properties Various improvements relating to surface / interface control such as chemical resistance are expected and various proposals have been made.

A cationic photopolymerizable resin such as an epoxy resin, which is one of these polymer materials, is a resin in which a polymerizable functional group undergoes a polymerization reaction by three-dimensional crosslinking upon irradiation with light such as ultraviolet rays.
This photo-cationic polymerizable resin can be cured without a solvent, and in addition, since it is not affected by oxygen during polymerization, it can be cured in the presence of air. Furthermore, since the energy required for curing is low, it can be said to be a useful resin from both the industrial and environmental aspects.
In addition, this cured product has excellent adhesion, chemical resistance, heat resistance and electrical insulation, and is used in various fields such as paints, electrical insulators and adhesives. In addition, it also has a feature of high transparency, and is often used in the optical field where high transparency is required, such as transparent insulating sealants for optoelectronics such as light emitting diodes.

As a surface modification method for these photo-cationic polymerizable resins, a novolak resin containing a fluoroalkyl group and a curing reactive group such as an epoxy group in the same molecule is replaced with a photo-cationic polymerizable resin such as a urethane acrylate resin or an epoxy resin. A method for adding antifouling property to the surface of the cured product is disclosed (Patent Document 1).
Further, a method of coating a fluorine-based polymer film single layer film on a thermosetting single resin lens for optical use using an acrylic / epoxy resin as a material is disclosed (Patent Document 2).
On the other hand, as one surface modification method of a polymer, a method is known in which a branched polymer is added to a matrix polymer composed of a linear polymer, and the branched polymer is concentrated on the surface of the matrix polymer (Patent Document 3).

International Publication No. 2008/146661 pamphlet JP 2010-224315 A International Publication No. 2007/0449608 Pamphlet

As described above, various surface modification of the photocationically polymerizable resin with the fluorine-containing polymer has been proposed. For example, Patent Document 1 mentions at all about the transparency that is a major feature of the cured photocationic polymerizable resin. Not. Moreover, in the method of patent document 2, it is necessary to carry out surface coating separately after hardening of resin used as a base material, and the process became complicated and industrially disadvantageous.
That is, a surface modifier that is fixed in the cured product and can be easily surface-modified without losing the original characteristics of the photocationically polymerizable resin cured product such as transparency, and a photocation containing the same There has been a need for a polymerizable composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a fluorine-containing highly branched polymer obtained by introducing a fluoroalkyl group into a highly branched polymer and introducing an alicyclic epoxy group or oxetanyl group. By adopting as a surface modifier for the photo-cationic polymerizable resin, it not only has excellent solubility in organic solvents, but also has excellent mixing and dispersibility in the photocationic polymerizable resin, which is a matrix resin, and aggregates in the matrix resin. The present invention was completed by finding that a cured product having high transparency and excellent surface modification properties can be obtained.

（式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²はヒドロキシ基で置換されていてもよい炭素原子数２乃至１２のフルオロアルキル基を表す。）
第９観点として、前記モノマーＢが下記式［２］で表される化合物である、第８観点に記載の含フッ素高分岐ポリマーに関する。

（式中、Ｒ¹は前記式［１］における定義と同じ意味を表し、Ｘは水素原子又はフッ素原子を表し、ｍは１又は２を表し、ｎは０乃至５の整数を表す。）
第１０観点として、前記モノマーＡに対して１０乃至３００モル％量の前記モノマーＣを用いて得られる、第１観点に記載の含フッ素高分岐ポリマーに関する。
第１１観点として、前記モノマーＣが、ビニル基又は（メタ）アクリル基の何れか一方又は双方を有する化合物である、第１０観点に記載の含フッ素高分岐ポリマーに関する。
第１２観点として、前記モノマーＣが下記式［３］で表される化合物である、第１１観点に記載の含フッ素高分岐ポリマーに関する。

（式中、Ｒ³は水素原子又はメチル基を表し、Ｌは単結合、又はエーテル結合もしくはエステル結合を含んでいてもよい炭素原子数１乃至６のアルキレン基を表す。）
第１３観点として、前記モノマーＣが下記式［４］で表される化合物である、第１１観点に記載の含フッ素高分岐ポリマーに関する。

（式中、Ｒ⁴は水素原子又はメチル基を表し、Ｒ⁵は水素原子又は炭素原子数１乃至６のアルキル基を表し、Ｌは単結合、又はエーテル結合もしくはエステル結合を含んでいてもよい炭素原子数１乃至６のアルキレン基を表す。）
第１４観点として、前記重合開始剤Ｄがアゾ系重合開始剤である、第１観点乃至第１３観点のうち何れか一項に記載の含フッ素高分岐ポリマーに関する。
第１５観点として、前記重合開始剤Ｄがジメチル１，１’−アゾビス（１−シクロヘキサンカルボキシレート）である、第１４観点に記載の含フッ素高分岐ポリマーに関する。
第１６観点として、さらに、前記モノマーＡのモル数に対して５乃至３００モル％量の下記式［５］で表されるモノマーＥを共重合させることにより得られる、第１４観点に記載の含フッ素高分岐ポリマーに関する。

（式中、Ｒ⁶は水素原子又はメチル基を表し、Ｒ⁷は炭素原子数６乃至３０のアルキル基又は炭素原子数３乃至３０の脂環基を表す。）
第１７観点として、第１観点乃至第１６観点のうち何れか一項に記載の含フッ素高分岐ポリマーからなる、光カチオン重合性樹脂の表面改質剤に関する。
第１８観点として、（ａ）第１観点乃至第１６観点のうち何れか一項に記載の含フッ素高分岐ポリマー、及び（ｂ）光カチオン重合性樹脂プレポリマーを含む、光カチオン重合性樹脂組成物に関する。
第１９観点として、前記（ｂ）プレポリマーの質量に対して０．００１乃至２０質量％の前記（ａ）含フッ素高分岐ポリマーを含む、第１８観点に記載の樹脂組成物に関する。
第２０観点として、前記（ｂ）プレポリマーが脂環式エポキシ基を少なくとも１つ有する化合物である、第１９観点に記載の樹脂組成物に関する。
第２１観点として、さらに（ｃ）光酸発生剤を含む、第１８観点に記載の樹脂組成物に関する。
第２２観点として、前記（ｂ）プレポリマーの質量に対して０．０５乃至３０質量％の前記（ｃ）光酸発生剤を含む、第２１観点に記載の樹脂組成物に関する。
第２３観点として、第１８観点乃至第２２観点のうち何れか一項に記載の樹脂組成物より得られる硬化物に関する。
第２４観点として、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にフルオロアルキル基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＢと、分子内に脂環式エポキシ基及びオキセタニル基からなる群から選ばれる少なくとも１個の光カチオン重合性基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＣとを、該モノマーＡのモル数に対して、５乃至２００モル％量の重合開始剤Ｄの存在下で重合させることを特徴とする、含フッ素高分岐ポリマーの製造方法に関する。That is, the present invention provides, as a first aspect, a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule. B and a monomer C having at least one photocationically polymerizable group and at least one radical polymerizable double bond selected from the group consisting of an alicyclic epoxy group and an oxetanyl group in the molecule, The present invention relates to a fluorine-containing highly branched polymer obtained by polymerizing in the presence of 5 to 200 mol% of a polymerization initiator D with respect to the number of moles.
As a 2nd viewpoint, the said monomer A is related with the fluorine-containing highly branched polymer as described in a 1st viewpoint which is a compound which has any one or both of a vinyl group or a (meth) acryl group.
As a 3rd viewpoint, the said monomer A is related with the fluorine-containing highly branched polymer as described in a 2nd viewpoint which is a divinyl compound or a di (meth) acrylate compound.
As a fourth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the third aspect, in which the monomer A is an alicyclic di (meth) acrylate.
As a fifth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the fourth aspect, in which the monomer A is tricyclodecane dimethanol di (meth) acrylate.
As a sixth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the first aspect, which is obtained using 5 to 300 mol% of the monomer B with respect to the monomer A.
As a 7th viewpoint, the said monomer B is related with the fluorine-containing highly branched polymer as described in a 6th viewpoint which is a compound which has any one or both of a vinyl group or a (meth) acryl group.
As an eighth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the seventh aspect, in which the monomer B is a compound represented by the following formula [1].

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a C 2-12 fluoroalkyl group which may be substituted with a hydroxy group.)
As a ninth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the eighth aspect, in which the monomer B is a compound represented by the following formula [2].

(Wherein R ¹ represents the same meaning as defined in Formula [1], X represents a hydrogen atom or a fluorine atom, m represents 1 or 2, and n represents an integer of 0 to 5).
As a 10th viewpoint, it is related with the fluorine-containing highly branched polymer as described in a 1st viewpoint obtained using the said monomer C of the 10 to 300 mol% quantity with respect to the said monomer A. FIG.
As an 11th viewpoint, the said monomer C is related with the fluorine-containing highly branched polymer as described in a 10th viewpoint which is a compound which has any one or both of a vinyl group or a (meth) acryl group.
As a twelfth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the eleventh aspect, in which the monomer C is a compound represented by the following formula [3].

(In the formula, R ³ represents a hydrogen atom or a methyl group, and L represents a single bond, or an alkylene group having 1 to 6 carbon atoms which may contain an ether bond or an ester bond.)
As a thirteenth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the eleventh aspect, in which the monomer C is a compound represented by the following formula [4].

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and L may include a single bond, an ether bond or an ester bond. Represents an alkylene group having 1 to 6 carbon atoms.)
As a fourteenth aspect, the present invention relates to the fluorine-containing highly branched polymer according to any one of the first aspect to the thirteenth aspect, in which the polymerization initiator D is an azo polymerization initiator.
As a fifteenth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the fourteenth aspect, in which the polymerization initiator D is dimethyl 1,1′-azobis (1-cyclohexanecarboxylate).
As a sixteenth aspect, the inclusion according to the fourteenth aspect, obtained by copolymerizing a monomer E represented by the following formula [5] in an amount of 5 to 300 mol% with respect to the number of moles of the monomer A, is provided. The present invention relates to a fluorine highly branched polymer.

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 6 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.)
As a seventeenth aspect, the present invention relates to a surface modifier for a photocationically polymerizable resin comprising the fluorine-containing highly branched polymer according to any one of the first aspect to the sixteenth aspect.
As an eighteenth aspect, a photocationically polymerizable resin composition comprising (a) the fluorine-containing highly branched polymer according to any one of the first aspect to the sixteenth aspect, and (b) a photocationically polymerizable resin prepolymer. Related to things.
As a nineteenth aspect, the present invention relates to the resin composition according to the eighteenth aspect, comprising 0.001 to 20% by mass of the (a) fluorine-containing highly branched polymer based on the mass of the (b) prepolymer.
As a twentieth aspect, the present invention relates to the resin composition according to the nineteenth aspect, in which the (b) prepolymer is a compound having at least one alicyclic epoxy group.
As a twenty-first aspect, the present invention relates to the resin composition according to the eighteenth aspect, further including (c) a photoacid generator.
As a twenty-second aspect, the present invention relates to the resin composition according to the twenty-first aspect, comprising 0.05 to 30% by mass of the (c) photoacid generator based on the mass of the (b) prepolymer.
As a 23rd viewpoint, it is related with the hardened | cured material obtained from the resin composition as described in any one of 18th viewpoint thru | or 22nd viewpoint.
As a twenty-fourth aspect, a monomer A having two or more radical polymerizable double bonds in the molecule, a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule, A monomer C having at least one photocationically polymerizable group and at least one radical polymerizable double bond selected from the group consisting of an alicyclic epoxy group and an oxetanyl group, relative to the number of moles of the monomer A The present invention relates to a method for producing a fluorine-containing highly branched polymer, wherein the polymerization is carried out in the presence of 5 to 200 mol% of a polymerization initiator D.

Since the fluorine-containing hyperbranched polymer of the present invention has positively introduced a branched structure, it has less entanglement between molecules compared to a linear polymer, exhibits fine particle behavior, solubility in an organic solvent, and resin. Is highly dispersible. For this reason, when the fluorine-containing highly branched polymer of the present invention is blended into a photocationically polymerizable resin composition or the like to produce a cured product, the particulate highly branched polymer easily moves to the interface (cured product surface). Thus, it is easy to impart activities such as peelability, water / oil repellency, and antifouling properties to the resin surface. In addition, the fluorine-containing highly branched polymer of the present invention has a photocationically polymerizable group in the molecule, so that when the photocationically polymerizable resin is selected as the matrix resin, it will be fixed when the resin is cured, The activity imparted to the resin surface can be immobilized. Moreover, the fluorine-containing highly branched polymer of the present invention has high mixing / dispersibility with the matrix resin, and can be mixed / dispersed without causing aggregation in the resin, producing a cured product with excellent transparency. it can.
Therefore, by adding a small amount of the fluorine-containing highly branched polymer of the present invention to the photocationic polymerizable composition, the surface of the cured photocationic polymerizable resin can be easily modified over a long period of time, and the transparency It can be set as a cured product excellent in.

1 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 1 produced in Example 1. FIG. 2 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 1 produced in Example 1. FIG. FIG. 3 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 2 produced in Example 2. 4 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 2 produced in Example 2. FIG. FIG. 5 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 3 produced in Example 3. 6 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 3 produced in Example 3. FIG. FIG. 7 is a diagram showing the ¹ H NMR spectrum of the hyperbranched polymer 4 produced in Example 4. FIG. 8 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 4 produced in Example 4. FIG. 9 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 5 produced in Example 5. 10 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 5 produced in Example 5. FIG. FIG. 11 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 6 produced in Comparative Example 1. 12 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 6 produced in Comparative Example 1. FIG. FIG. 13 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 7 produced in Comparative Example 2. FIG. 14 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 7 produced in Comparative Example 2. 15 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 8 produced in Example 18. FIG. FIG. 16 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 9 produced in Example 19. FIG. 17 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 10 produced in Example 20. 18 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 11 produced in Example 21. FIG. FIG. 19 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 12 produced in Example 22. 20 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 13 produced in Example 23. FIG. FIG. 21 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 14 produced in Example 24.

<Fluorine-containing highly branched polymer>
The fluorine-containing highly branched polymer of the present invention comprises a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule. A monomer C having at least one photocationically polymerizable group and at least one radical polymerizable double bond selected from the group consisting of an alicyclic epoxy group and an oxetanyl group in the molecule, and a monomer described later if desired E is a polymer obtained by polymerizing E in the presence of a polymerization initiator D in an amount of 5 to 200 mol% based on the number of moles of the monomer A. The fluorine-containing highly branched polymer of the present invention is a so-called initiator fragment-incorporating type fluorine-containing highly branched polymer, and has a polymerization initiator D fragment used for polymerization at its terminal.

[Monomer A]
In the present invention, the monomer A having two or more radically polymerizable double bonds in the molecule preferably has one or both of a vinyl group and a (meth) acryl group, and in particular, a divinyl compound or di (meta). ) An acrylate compound is preferred. In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of such a monomer A include organic compounds shown in the following (A1) to (A7).
(A1) Vinyl hydrocarbon:
(A1-1) Aliphatic vinyl hydrocarbons; isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene (A1-2) Alicyclic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc. (A1-3) aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene , Divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine, etc. (A2) Vinyl esters, allyl esters, vinyl ethers, allyl ethers, vinyl ketones:
(A2-1) vinyl ester; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate, etc. (A2-2) allyl ester; diallyl maleate, diallyl phthalate, Diallyl isophthalate, diallyl adipate, allyl (meth) acrylate, etc. (A2-3) vinyl ether; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc. (A2-4) allyl ether; diallyl ether, diallyloxyethane, tri Allyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc. (A2-5) vinyl ketone; divinyl ketone, diallyl Tons, etc. (A3) (meth) acrylic acid ester:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkoxytitanium tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) ) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decanedimethanol di ( Acrylate), dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4 -(2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecylenoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl ] Sulphides, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, etc. (A4) Vinyl compounds having a polyalkylene glycol chain:
Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, etc. (A5) Nitrogen-containing vinyl compounds:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylenebis (meth) acrylamide, bismaleimide, etc. (A6) silicon-containing vinyl compounds:
Dimethyldivinylsilane, divinylmethylphenylsilane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane (A7) fluorine-containing vinyl compounds such as dietoxydivinylsilane:
1,4-divinylperfluorobutane, 1,4-divinyloctafluorobutane, 1,6-divinylperfluorohexane, 1,6-divinyldodecafluorohexane, 1,8-divinylperfluorooctane, 1,8-divinyl Hexadecafluorooctane, etc.

Among these, preferred are the aromatic vinyl hydrocarbon compounds of the above group (A1-3), vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the group (A2), (meth) acrylic of the group (A3). An acid ester, a vinyl compound having a polyalkylene glycol chain of (A4) group, and a nitrogen-containing vinyl compound of (A5) group. Particularly preferred are divinylbenzene belonging to group (A1-3), diallyl phthalate belonging to group (A2), ethylene glycol di (meth) acrylate belonging to group (A3), 1,3-adamantane dimethanol di (meta). ) Acrylate, tricyclo [5.2.1.0 ^2,6 ] decandimethanol di (meth) acrylate, and methylenebis (meth) acrylamide belonging to group (A5). Among these, divinylbenzene, ethylene glycol di (meth) acrylate and tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate are preferable, and tricyclo [5.2.1.0 ^{2, 6} ] Decanedimethanol di (meth) acrylate is more preferred.

[Monomer B]
In the present invention, the monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule preferably has either one or both of a vinyl group and a (meth) acryl group, particularly The compound represented by the formula [1] is preferable, and the compound represented by the formula [2] is more preferable.

  Examples of such monomer B include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl ( (Meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3 -Methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetra Fluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoro Pentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) Acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluoro Octyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) Acrylate And 3- (perfluoro-7-methyl-octyl) -2-hydroxypropyl (meth) acrylate.

  In the present invention, the amount of the monomer B used is 5 to 300 mol%, particularly 10 to 150 mol%, based on the number of moles of the monomer A used, from the viewpoint of reactivity and the surface modification effect derived from the fluoroalkyl group. More preferably, it is used in an amount of 20 to 100 mol%.

[Monomer C]
In the present invention, the monomer C having at least one photocationically polymerizable group and at least one radical polymerizable double bond selected from the group consisting of an alicyclic epoxy group and an oxetanyl group in the molecule is preferably vinyl. It is preferable to have either one or both of a group and a (meth) acryl group, and it is particularly preferable that the compound is represented by the compound represented by the formula [3] or the compound represented by the formula [4].

Such a monomer C includes 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 3,4-epoxy-1-hydroxycyclohexyl group, 3,4-epoxy-6 as a photocationically polymerizable group. Examples thereof include compounds having an alicyclic epoxy group such as a -methylcyclohexyl group; an oxetanyl group such as a 3-oxetanyl group, a 3-methyl-3-oxetanyl group, and a 3-ethyl-3-oxetanyl group.
In particular, the compound represented by the formula [3] includes 2,3-epoxycyclopentylmethyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2 -(3,4-epoxycyclohexyl) ethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) -2-hydroxyethyl (meth) acrylate and the like.
Examples of the compound represented by the formula [4] include (3-methyloxetane-3-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) (meth) acrylate, and (oxetane-3- Yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, and the like.

  In the present invention, the amount of the monomer C used is 10 to 300 mol%, particularly 20 to 200 mol%, based on the number of moles of the monomer A used, from the viewpoint of reactivity and dispersibility in the photocationic curable resin. More preferably, it is used in an amount of 30 to 150 mol%.

[Polymerization initiator D]
As the polymerization initiator D in the present invention, an azo polymerization initiator is preferably used. Examples of the azo polymerization initiator include compounds shown in the following (1) to (6).
(1) Azonitrile compound:
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis ( 1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile and the like;
(2) Azoamide compound:
2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- ( 1-hydroxybutyl)] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propenyl) -2- Methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like;
(3) Cyclic azoamidine compound:
2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride and the like;
(4) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, etc .;
(5) Other:
Dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis (1-acetoxy- 1-phenylethane), dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), 4,4′-azobis (4-cyanopentanoic acid) and the like.
(6) Fluoroalkyl group-containing azo polymerization initiator 4,4′-azobis (2-cyanopentanoic acid 2- (perfluoromethyl) ethyl), 4,4′-azobis (4-cyanopentanoic acid 2- ( Perfluorobutyl) ethyl), 4,4′-azobis (2-cyanopentanoic acid 2- (perfluorohexyl) ethyl) and the like.

  Among the azo polymerization initiators, 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobisisobutyrate or dimethyl 1,1 from the viewpoint of dispersibility in a photocationic curable resin. '-Azobis (1-cyclohexanecarboxylate) is preferred, and dimethyl 1,1'-azobis (1-cyclohexanecarboxylate) is particularly preferred.

  The polymerization initiator D is used in an amount of 5 to 200 mol%, preferably 20 to 200 mol%, more preferably 20 to 100 mol%, based on the number of moles of the monomer A. .

[Monomer E]
In the fluorine-containing highly branched polymer of the present invention, in addition to the aforementioned monomer A, monomer B and monomer C, the compound represented by the above formula [5] as the monomer E, that is, having 6 to 30 carbon atoms in the molecule A monomer having an alkyl group or an alicyclic group having 3 to 30 carbon atoms and a (meth) acryl group may be included. By including the monomer E, surface modification properties such as excellent mold releasability can be imparted to the coating film obtained from the resin composition containing the fluorine-containing highly branched polymer of the present invention.

Examples of the alkyl group having 6 to 30 carbon atoms include hexyl group, ethylhexyl group, 3,5,5-trimethylhexyl group, heptyl group, octyl group, 2-octyl group, isooctyl group, nonyl group, decyl group, isodecyl group. Group, undecyl group, lauryl group, tridecyl group, myristyl group, palmityl group, stearyl group, isostearyl group, aralkyl group, behenyl group, lignoceryl group, serotoyl group, montanyl group, melicyl group and the like.
Among them, the number of carbon atoms of the alkyl group is preferably 10 to 30 and more preferably 16 to 24 from the viewpoint of the surface modification effect.

Examples of the alicyclic group having 3 to 30 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, isobornyl group, norbornenyl group, menthyl group, adamantyl group, tricyclo group. And [5.2.1.0 ^2,6 ] decanyl group.
Among these, from the viewpoint of the surface modification effect, an alicyclic group having 3 to 14 carbon atoms is preferable, and an alicyclic group having 6 to 12 carbon atoms is more preferable.

Examples of such a monomer E include hexyl (meth) acrylate, ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-octyl ( (Meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, palmityl (meth) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, Lopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornene (meth) acrylate, menthyl (meth) acrylate, adamantane (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane (meth) acrylate and the like. These monomers E may be used alone or in combination of two or more.

  In the present invention, the monomer E is preferably used in an amount of 5 to 300 mol%, particularly 10 to 150 mol%, based on the number of moles of the monomer A used, from the viewpoint of reactivity and surface modification effect. It is preferable to do.

<Method for producing fluorine-containing highly branched polymer>
The fluorine-containing highly branched polymer of the present invention is obtained by polymerizing the aforementioned monomer A, monomer B, monomer C and optionally monomer E in the presence of a predetermined amount of polymerization initiator D with respect to monomer A, Examples of the polymerization method include known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, and bulk polymerization. Among these, solution polymerization or precipitation polymerization is preferable. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.
In addition, the manufacturing method of a fluorine-containing highly branched polymer is also the object of the present invention.

Examples of organic solvents used here include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane Solvent: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and other ester or ester ether solvents; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cello Ether solvents such as rub, butyl cellosolve, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, iso Alcohol solvents such as butanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; N -Heterocyclic compound type | system | group solvents, such as methyl-2-pyrrolidone, and these 2 or more types of mixed solvents are mentioned.
Of these, aromatic hydrocarbon solvents, halogen solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, etc. are preferred, with benzene, toluene, xylene being particularly preferred. Orthodichlorobenzene, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, n-butanol, Isobutanol, tert-butanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

When the polymerization reaction of the present invention is carried out in the presence of an organic solvent, the mass of the organic solvent relative to 1 part by mass of the monomer A is usually 5 to 120 parts by mass, preferably 10 to 110 parts by mass.
The polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N _2.
The polymerization temperature is arbitrary as long as it is not higher than the boiling point of the reaction mixture, but is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. or higher and 150 ° C. or lower, from the viewpoint of polymerization efficiency and molecular weight control. More preferably, the temperature is from 130 ° C to 130 ° C.
The reaction time varies depending on the reaction temperature, the types and ratios of the monomer A, the monomer B, the monomer C, the monomer E and the polymerization initiator D, the polymerization solvent type, etc., but cannot be defined unconditionally, but preferably 30 Min. To 720 min., More preferably 40 min. To 540 min.
After completion of the polymerization reaction, the obtained fluorine-containing hyperbranched polymer is recovered by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.

  The weight average molecular weight (Mw) measured in terms of polystyrene by gel permeation chromatography of the fluorine-containing highly branched polymer of the present invention is 1,000 to 400,000, preferably 2,000 to 200,000.

<Surface modifier and photocationically polymerizable resin composition>
The fluorine-containing highly branched polymer of the present invention is useful as a surface modifier for a photocationically polymerizable resin, and the surface modifier is also an object of the present invention.
The present invention also relates to a photocationically polymerizable resin composition comprising the aforementioned (a) fluorine-containing highly branched polymer and (b) a photocationically polymerizable resin prepolymer.

[(B) Photocationically polymerizable resin prepolymer]
The (b) photocationically polymerizable resin prepolymer is not particularly limited as long as it is a compound having at least one, preferably 2 to 10, photocationically polymerizable sites in the molecule. The prepolymer in the present invention means a compound that is not a so-called high molecular substance, and includes not only a monomer compound (monomer) in a narrow sense but also a dimer, trimer, oligomer, and reactive polymer. Is also included.
Examples of the compound having a cationic photopolymerizable moiety include compounds having a cyclic ether structure such as an epoxy ring and an oxetane ring, a vinyl ether structure, a vinyl thioether structure, and the like.
Among these compounds, compounds having at least one alicyclic epoxy group, for example, compounds having at least one epoxycyclohexane ring, epoxycyclopentane ring and the like are preferable.

  Examples of such (b) photocationically polymerizable resin prepolymer include bis (2,3-epoxycyclopentyl) ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane, and 3,4-epoxy-6. -Methylcyclohexyl 3 ', 4'-epoxy-6-methylcyclohexanecarboxylate, di (3,4-epoxycyclohexylmethyl) hexanedioate, di (3,4-epoxy-6-methylcyclohexylmethyl) hexanedioate, Ethylene bis (3,4-epoxycyclohexanecarboxylate), ethanediol di (3,4-epoxycyclohexylmethyl) ether, vinylcyclohexene dioxide, dicyclopentadiene diepoxide, 2- (3,4-epoxycyclohexyl-5, 5-spiro-3,4- Poxy) cyclohexane-1,3-dioxane, 2,2′-bis (3,4-epoxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate, 1, 2: 8, 9-diepoxylimonene, epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone, 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, 3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) Methyl] benzene, [1- (3-ethyl-3-oxetani Lmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobomyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobomyl (3-ethyl-3-oxetanylmethyl) Ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxy Ethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromo Enyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromo Phenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3 -Ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) A , Trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3,3- [1,4-phenylenebis (methyleneoxymethylene)] bis (3-ethyloxetane), 3-ethyl- 3-hydroxymethyl oxetane, bis [(1-ethyl (3-oxetanyl) methyl)] ether, and the like can be given.

  In the photocationically polymerizable resin composition of the present invention, the blending amounts of (a) a fluorine-containing highly branched polymer and (b) a photocationically polymerizable resin prepolymer are as follows. That is, (a) the fluorine-containing hyperbranched polymer is preferably 0.001% by mass to 20% by mass, particularly 0.005% by mass to 15% by mass, and more preferably 0.8% by mass with respect to the mass of (b) the prepolymer. The content is preferably 01% by mass to 10% by mass.

[(C) Photoacid generator]
The photocationically polymerizable resin composition of the present invention may further contain (c) a photoacid generator.
The photoacid generator (c) is not particularly limited as long as it generates an acid directly or indirectly by light irradiation. For example, sulfonic acid compounds and other sulfonic acid derivatives, diazomethane compounds, onium salt compounds, Examples include sulfonimide compounds, disulfone compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without any particular limitation. The photoacid generator of component (c) may be used alone or in combination of two or more.

ジフェニルヨードニウムクロリド、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムメシレート、ジフェニルヨードニウムトシレート、ジフェニルヨードニウムブロミド、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムヘキサフルオロアルセネート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムメシレート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムトシレート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムテトラフルオロボレート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムクロリド、ビス（ｐ−クロロフェニル）ヨードニウムクロリド、ビス（ｐ−クロロフェニル）ヨードニウムテトラフルオロボレート、トリフェニルスルホニウムクロリド、トリフェニルスルホニウムブロミド、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリ（ｐ−メトキシフェニル）スルホニウムテトラフルオロボレート、トリ（ｐ−メトキシフェニル）スルホニウムヘキサフルオロホスホネート、トリ（ｐ−エトキシフェニル）スルホニウムテトラフルオロボレート、トリフェニルホスホニウムクロリド、トリフェニルホスホニウムブロミド、トリ（ｐ−メトキシフェニル）ホスホニウムテトラフルオロボレート、トリ（ｐ−メトキシフェニル）ホスホニウムヘキサフルオロホスホネート、トリ（ｐ−エトキシフェニル）ホスホニウムテトラフルオロボレート、

Specific examples of the photoacid generator include the following. However, these compounds are examples of a very large number of applicable photoacid generators, and are of course not limited thereto.

Diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p-tert- Butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis ( p-tert-butylphenyl) iodoniumtetraf Oroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium trifluoromethanesulfonate , Tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p -Methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phospho Phosphonium hexafluorophosphonate, tri (p- ethoxyphenyl) phosphonium tetrafluoroborate,

Of these, onium salt compounds are useful. Specifically, aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate; diphenyliodonium hexafluoro Diaryl iodonium salts such as antimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium Hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate Diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4′-bis (diphenylsulfonio) phenyl sulfide bishexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide bishexafluorophosphate, 4 , 4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide bishexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide bishexafluorophosphate, 4- [4 ′-(benzoyl) phenylthio] phenyldi (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4 ′-(benzoyl) phenylthio] phenyldi (4-fluorophenyl) Such as hexafluorophosphate triarylsulfonium salts, and the like.
The above-mentioned onium salt derivatives are available as commercial products. For example, CPI-100P, CPI-100A, CPI-200K, CPI-200S (manufactured by San Apro Co., Ltd.), Adekaoptomer SP-150, SP -151, SP-170, SP-171 (manufactured by ADEKA, Inc.), Irgacure 261 (manufactured by BASF (formerly Ciba Specialty Chemicals)), and the like.
The (c) photoacid generator is in an amount of 0.05 to 30% by mass, preferably in an amount of 0.1 to 20% by mass, more preferably relative to the (b) photocationically polymerizable resin prepolymer. Can be used in an amount of 0.1 to 10% by weight.

[Other additives]
In addition, additives that are generally added as necessary to the photocationically polymerizable resin composition of the present invention, such as a photosensitizer, a polymerization inhibitor, and a polymerization start, unless the effects of the present invention are impaired. Agents, leveling agents, surfactants, adhesion promoters, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, and the like may be appropriately blended. Moreover, you may mix a solvent as needed.

<Hardened product>
The photocationically polymerizable resin composition of the present invention can be cured by photopolymerization (curing) after filling a predetermined mold. Preferably, the polymerization can be completed by post-baking after photopolymerization, specifically by heating using a hot plate, oven or the like.
The thickness of the bulk body (molded product) thus obtained is usually 0.02 to 10 mm, preferably 0.5 to 5 mm after drying and curing.

The photocationically polymerizable resin composition of the present invention can also form a cured product (molded product) such as a cured film or a laminate by coating on a substrate and photopolymerizing (curing) it.
Examples of the base material in this case include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, Slate etc. can be mentioned. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
The coating method on the substrate is cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen). Printing, etc.) can be selected as appropriate, and in particular, since it can be applied in a short time, it can be used even in a highly volatile solution, and the spin coating method is used because it can be applied with high uniformity. It is desirable. It is preferable that the cationic photopolymerizable resin composition is filtered in advance using a filter having a pore diameter of about 0.2 μm in advance and then used for coating.
When coating, a solvent may be added to the resin composition as necessary to form a varnish. For example, acetone, tetrahydrofuran (THF), toluene, N, N-dimethylformamide (DMF), cyclohexanone, propylene glycol A varnish is formed using a solvent such as monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, ethyl lactate, diethylene glycol monoethyl ether, butyl cellosolve, and γ-butyrolactone.
After coating, preferably followed by preliminary drying with a hot plate or oven, etc., followed by irradiation with actinic rays such as ultraviolet rays for photocuring. Examples of actinic rays include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like can be used.
Thereafter, post-baking is performed, and specifically, the polymerization can be completed by heating using a hot plate, an oven or the like.
The thickness of the film formed by coating is usually 0.01 to 50 μm, preferably 0.05 to 20 μm after drying and curing.

  As described above, the cured product of the present invention is in a state in which more of the fluorine-containing highly branched polymer is present on the cured product surface (interface) than in the cured product (deep part). For this reason, for various machines such as mixing / molding machines used in the production of cured products and mold releasability, releasability from other resin molded products such as films, and water / oil repellency and antifouling properties. An excellent cured product can be obtained.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) Gel permeation chromatography (GPC)
Device: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L, KF-805L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: RI
(2) ¹ H NMR spectrum and ¹³ C NMR spectrum Apparatus: JNM-ECA700 manufactured by JEOL Ltd.
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (3) ion chromatography (fluorine quantitative analysis)
Device: ICS-1500, manufactured by Nippon Dionex Co., Ltd.
Solvent: (2.7 mmol Na ₂ CO ₃ + 0.3 mmol NaHCO ₃ ) / L aqueous solution Detector: Electrical conductivity (4) Spin coater Device: MS-A100 manufactured by Mikasa Corporation
(5) Ellipsometry (refractive index and film thickness measurement)
Apparatus: J.M. A. EC-400 manufactured by Woollam
(6) Contact angle measurement device: VCA Optima manufactured by AST Products
Measurement temperature: 20 ° C
Measurement method: The measurement medium was dropped onto the surface to be measured, the contact angle after 10 seconds was measured 5 times, and the average value of three values excluding the maximum value and the minimum value was defined as the contact angle value.
(7) Glass transition temperature (Tg) measurement Device: DSC204 F1 Phoenix (registered trademark) manufactured by NETZSCH
Measurement conditions: Under a nitrogen atmosphere Temperature rising rate 1: 30 ° C./min (25-200 ° C.) (Examples 1, 3, 4, 5, Comparative Example 1)
Temperature rising rate 2: 5 ° C./min (25 to 160 ° C.) (Example 2, Comparative Example 2)
Temperature increase rate 3: 10 ° C./min (0 to 150 ° C.) (Examples 18 to 24)
(8) 5% weight loss temperature (Td _5% ) measurement device: TG8120 manufactured by Rigaku Corporation
Measurement conditions: In air atmosphere Temperature rising rate: 10 ° C / min (25-500 ° C)
(9) UV irradiation device Device: H02-L41 manufactured by Eye Graphics Co., Ltd.
Intensity: 16 mW / cm ² (365 nm)
(10) Haze meter (turbidity measurement)
Device: NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

Abbreviations represent the following meanings.
DCP: Tricyclo [5.2.1.0 ^2,6 ] decane dimethanol dimethacrylate [DCP manufactured by Shin-Nakamura Chemical Co., Ltd.]
EGDMA: Ethylene glycol dimethacrylate [1G made by Shin-Nakamura Chemical Co., Ltd.]
C6FA: 2- (perfluorohexyl) ethyl acrylate [R-1620 manufactured by Daikin Industries, Ltd.]
3FEA: 2,2,2-trifluoroethyl acrylate [V-3F, manufactured by Osaka Organic Chemical Industry Co., Ltd.]
OXMA: (3-Ethyloxetane-3-yl) methyl methacrylate [Ethanacol, manufactured by Ube Industries, Ltd.]
CYM: 3,4-epoxycyclohexylmethyl methacrylate [Cyclomer M100 manufactured by Daicel Corporation]
GMA: Glycidyl methacrylate [Pure Chemical Co., Ltd.]
STA: stearyl acrylate [Osaka Organic Chemical Co., Ltd. STA]
ISTA: Isostearyl acrylate [ISTA made by Osaka Organic Chemical Industry Co., Ltd.]
LA: Lauryl acrylate [LA manufactured by Osaka Organic Chemical Industry Co., Ltd.]
BA: Behenyl acrylate [Shin-Nakamura Chemical Co., Ltd. A-BH]
DCHC: Dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) [VE-073 manufactured by Wako Pure Chemical Industries, Ltd.]
MAIB: Dimethyl 2,2′-azobisisobutyrate [MAIB manufactured by Otsuka Chemical Co., Ltd.]
AMBN: 2,2′-azobis (2-methylbutyronitrile) [V-59 manufactured by Wako Pure Chemical Industries, Ltd.]
CEL2021P: 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate [Celoxide 2021P manufactured by Daicel Corporation]
CEL3000: 1, 2: 8,9-diepoxy limonene [Celoxide 3000 manufactured by Daicel Corporation]
GT401: Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone [Epolyde GT401 manufactured by Daicel Corporation]
CPI-100P: Diphenyl (4- (phenylthio) phenyl) sulfonium hexafluorophosphate (V) (CPI-100P manufactured by San Apro Co., Ltd.)
MIBK: methyl isobutyl ketone PGME: propylene glycol monomethyl ether DO: 1,4-dioxane

[Example 1] Synthesis of hyperbranched polymer 1 In a 300 mL reaction flask, 67 g of MIBK was charged, and nitrogen was poured for 5 minutes while stirring, and the mixture was heated until the internal solution was refluxed (approximately 116 ° C).
Into another 200 mL reaction flask, DCP 6.7 g (20 mmol), C6FA 4.2 g (10 mmol), OXMA 1.8 g (10 mmol), DCHC 3.7 g (12 mmol) and MIBK 67 g were charged, and nitrogen was poured for 5 minutes while stirring. And heated until the liquid temperature reached about 35 ° C.
The contents were dripped from the 200 mL reaction flask charged with DCP, C6FA, OXMA, and DCHC into the refluxed MIBK in the 300 mL reaction flask using a dropping pump over 25 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, 45 g of MIBK was distilled off from this reaction solution using a rotary evaporator, and then added to 465 g of methanol at 0 ° C. to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 7.5 g of the target product (highly branched polymer 1) as a white powder (yield 47%).
¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 1 and 2. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target product was 3,700, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 2.1.

[Example 2] Synthesis of hyperbranched polymer 2 A 300 mL reaction flask was charged with 67 g of MIBK, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
Into another 200 mL reaction flask, DCP 6.7 g (20 mmol), C6FA 4.2 g (10 mmol), CYM 2.0 g (10 mmol), DCHC 3.7 g (12 mmol) and MIBK 74 g were charged, and nitrogen was poured for 5 minutes with stirring to replace nitrogen. And heated until the liquid temperature reached about 35 ° C.
The contents were dripped from the 200 mL reaction flask charged with DCP, C6FA, CYM and DCHC into the refluxed MIBK in the above 300 mL reaction flask using a dropping pump over 35 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, 61 g of MIBK was distilled off from this reaction solution using a rotary evaporator, and then added to 470 g of methanol at 0 ° C. to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 9.9 g of the desired product (highly branched polymer 2) as a white powder (yield 73%).
The ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 3 and 4. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 5,300, and dispersion degree: Mw / Mn was 1.9.

[Example 3] Synthesis of hyperbranched polymer 3 A 300 mL reaction flask was charged with 67 g of MIBK, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately a temperature of 116 ° C).
Into another 200 mL reaction flask, DCP 6.7 g (20 mmol), C6FA 4.2 g (10 mmol), CYM 2.0 g (10 mmol), MAIB 2.8 g (12 mmol) and MIBK 67 g were charged, and nitrogen was poured for 5 minutes with stirring to replace nitrogen. And cooled to 5 ° C. in an ice bath.
The contents were added dropwise from the 200 mL reaction flask charged with DCP, C6FA, CYM and MAIB into the refluxed MIBK in the 300 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, 58 g of MIBK was distilled off from this reaction solution using a rotary evaporator, and then added to a mixed solution of 277 g of hexane and 44 g of ethanol to precipitate a polymer, and the supernatant was decanted. The remaining precipitate was redissolved using 7 g of MIBK, and the MIBK solution of this polymer was added to 202 g of methanol to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 5.2 g of the target product (highly branched polymer 3) as a white powder (yield 41%).
¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 5 and 6. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 4,700, and dispersion degree: Mw / Mn was 1.6.

[Example 4] Synthesis of hyperbranched polymer 4 A 300 mL reaction flask was charged with 67 g of MIBK, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
Into another 200 mL reaction flask was charged DCP 6.7 g (20 mmol), C6FA 4.2 g (10 mmol), CYM 2.0 g (10 mmol), AMBN 2.5 g (12 mmol) and MIBK 67 g, and nitrogen was purged for 5 minutes while stirring. And cooled to 7 ° C. in an ice bath.
The contents were added dropwise from the 200 mL reaction flask charged with DCP, C6FA, CYM and AMBN into the refluxed MIBK in the 300 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, 47 g of MIBK was distilled off from this reaction solution using a rotary evaporator, and then added to 379 g of methanol to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and vacuum dried to obtain 4.8 g of the target product (highly branched polymer 4) as a white powder (yield 38%).
¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 5,700, and dispersion degree: Mw / Mn was 2.0.

[Example 5] Synthesis of hyperbranched polymer 5 Into a 200 mL reaction flask, 40 g of MIBK was charged, and nitrogen was poured for 5 minutes while stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
In a separate 100 mL reaction flask, EGDMA 4.0 g (20 mmol), C6FA 4.2 g (10 mmol), CYM 2.0 g (10 mmol), MAIB 2.8 g (12 mmol) and MIBK 40 g were charged, and nitrogen was poured for 5 minutes while stirring. And cooled to 5 ° C. in an ice bath.
The contents were added dropwise from the 200 mL reaction flask charged with EGDMA, C6FA, CYM and MAIB into the refluxed MIBK in the 200 mL reaction flask using a dropping pump over 40 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, 33 g of MIBK was distilled off from this reaction solution using a rotary evaporator, and then added to 284 g of methanol to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and vacuum dried to obtain 6.0 g of the desired product (highly branched polymer 5) as a white powder (yield 59%).
The ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 9 and 10. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 6,700, and dispersion degree: Mw / Mn was 2.0.

[Example 18] Synthesis of hyperbranched polymer 8 A 200 mL reaction flask was charged with 67 g of MIBK, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
Into another 100 mL reaction flask, DCP6.8 g (20 mmol), C6FA 4.2 g (10 mmol), CYM 2.0 g (10 mmol), STA 3.3 g (10 mmol), MAIB 2.8 g (12 mmol) and MIBK 67 g were charged and stirred. Nitrogen was introduced for 5 minutes to perform nitrogen substitution, and the mixture was stirred at room temperature (17 ° C.) to dissolve each monomer.
The contents were added dropwise from the 100 mL reaction flask charged with DCP, C6FA, CYM, STA and MAIB to the refluxed MIBK in the aforementioned 200 mL reaction flask over 45 minutes using a dropping pump. . After completion of dropping, the mixture was aged for 70 minutes.
Next, 118 g of MIBK was distilled off from this reaction solution using a rotary evaporator, and then dropped into 227 g of methanol at 0 ° C. to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 11.6 g of a target product (highly branched polymer 8) as a transparent glassy solid (yield 90%).
FIG. 15 shows the ¹³ C NMR spectrum of the obtained target product. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 5,000, and dispersion degree: Mw / Mn was 1.7.

[Example 19] Synthesis of hyperbranched polymer 9 A 200 mL reaction flask was charged with 67 g of MIBK, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
In another 100 mL reaction flask, DCP 6.8 g (20 mmol), C6FA 4.2 g (10 mmol), CYM 2.1 g (11 mmol), ISTA 3.3 g (10 mmol), MAIB 2.8 g (12 mmol) and MIBK 67 g were charged with stirring. Nitrogen was introduced for 5 minutes to replace the nitrogen, and the mixture was stirred under ice cooling (5 ° C.) to dissolve each monomer.
The contents were added dropwise from the 100 mL reaction flask charged with DCP, C6FA, CYM, ISTA and MAIB to the refluxed MIBK in the aforementioned 200 mL reaction flask over 25 minutes using a dropping pump. . After completion of dropping, the mixture was aged for 90 minutes.
Next, 116 g of MIBK was distilled off from the reaction solution using a rotary evaporator, and the resulting solution was added dropwise to 203 g of methanol at 0 ° C. to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 7.6 g of the desired product (hyperbranched polymer 9) as a white solid (yield 59%).
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 6,700, and dispersion degree: Mw / Mn was 2.2.

[Example 20] Synthesis of hyperbranched polymer 10 A 200 mL reaction flask was charged with 67 g of MIBK, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
In another 100 mL reaction flask, DCP 6.7 g (20 mmol), C6FA 4.2 g (10 mmol), CYM 2.0 g (10 mmol), LA 2.4 g (10 mmol), MAIB 2.8 g (12 mmol) and MIBK 67 g were charged with stirring. Nitrogen was introduced for 5 minutes to replace the nitrogen, and the mixture was stirred under ice cooling (7 ° C.) to dissolve each monomer.
From the 100 mL reaction flask charged with DCP, C6FA, CYM, LA, and MAIB into the refluxed MIBK in the 200 mL reaction flask, the contents were added dropwise over 20 minutes using a dropping pump. . After completion of dropping, the mixture was aged for 60 minutes.
Next, 112 g of MIBK was distilled off from this reaction liquid using a rotary evaporator, and the resulting solution was added dropwise to 203 g of methanol at 0 ° C. to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 9.4 g of the desired product (highly branched polymer 10) as a white powder (yield 73%).
FIG. 17 shows the ¹³ C NMR spectrum of the obtained target product. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 6,700, and dispersion degree: Mw / Mn was 2.2.

[Example 21] Synthesis of hyperbranched polymer 11 A 200 mL reaction flask was charged with 67 g of MIBK, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
In another 100 mL reaction flask, DCP 6.7 g (20 mmol), C6FA 4.4 g (11 mmol), CYM 2.0 g (10 mmol), BA 3.7 g (10 mmol), MAIB 2.8 g (12 mmol), MIBK 67 g and toluene 12 g were charged. Nitrogen was introduced for 5 minutes while stirring to perform nitrogen substitution, and each monomer was dissolved by heating and stirring at an internal temperature of 30 ° C.
From the 100 mL reaction flask charged with DCP, C6FA, CYM, BA, and MAIB into the refluxed MIBK in the 200 mL reaction flask, the contents were added dropwise over 30 minutes using a dropping pump. . After completion of dropping, the mixture was aged for 70 minutes.
Next, 127 g of a mixed solution of MIBK and toluene was distilled off from this reaction solution using a rotary evaporator, and then dropped into 243 g of methanol at 0 ° C. to precipitate a polymer, and the supernatant was removed by decantation. To 20 g of the obtained viscous solid, 11 g of toluene was added to make it uniform, and then dropped again into 111 g of methanol at 0 ° C. to precipitate a polymer, which was purified by decantation. The obtained viscous product was dried to quantitatively obtain 13 g of the desired product (hyperbranched polymer 11) as a milky white viscous product.
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target product was 6,800, and the degree of dispersion: Mw / Mn was 1.8.

[Example 22] Synthesis of hyperbranched polymer 12 A 100 mL reaction flask was charged with 33 g of MIBK, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
In another 50 mL reaction flask, DCP 3.4 g (10 mmol), C6FA 2.1 g (5 mmol), OXMA 0.9 g (5 mmol), STA 1.6 g (5 mmol), MAIB 1.4 g (6 mmol) and MIBK 34 g were charged and stirred. Nitrogen was introduced for 5 minutes to replace the nitrogen, and the mixture was stirred under ice cooling (internal temperature 5 ° C.) to dissolve each monomer.
The contents were added dropwise from the 50 mL reaction flask charged with DCP, C6FA, OXMA, STA and MAIB to the refluxed MIBK in the 100 mL reaction flask using a dropping pump over 30 minutes. . After completion of dropping, the mixture was aged for 60 minutes.
Next, 63 g of MIBK was distilled off from the reaction solution using a rotary evaporator, 6 g of MIBK was added again, and the resulting solution was added dropwise to 157 g of methanol at 0 ° C. to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 3.0 g of the desired product (highly branched polymer 12) as a white powder (yield 47%).
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 6,900, and dispersion degree: Mw / Mn was 2.0.

[Example 23] Synthesis of hyperbranched polymer 13 A 200 mL reaction flask was charged with 34 g of a MIBK-toluene mixed solvent (mass ratio 1: 1), and nitrogen was allowed to flow for 5 minutes while stirring until the internal liquid was refluxed (approximately (Temperature 105 ° C.)
In another 100 mL reaction flask, DCP 3.3 g (10 mmol), C6FA 2.2 g (6 mmol), CYM 1.1 g (6 mmol), STA 1.6 g (5 mmol), DCHC 1.5 g (5 mmol) and MIBK-toluene mixed solvent (mass) (1: 1) 36 g was charged, and nitrogen was introduced for 5 minutes while stirring to perform nitrogen substitution.
From the 100 mL reaction flask in which DCP, C6FA, CYM, STA and DCHC were charged in the refluxing MIBK-toluene mixed solvent in the 200 mL reaction flask, the contents were removed using a dropping pump for 25 minutes. It was dripped over. After completion of dropping, the mixture was aged for 60 minutes.
Next, 61 g of the MIBK-toluene mixed solvent was distilled off from the reaction solution using a rotary evaporator, and the resulting solution was added dropwise to 101 g of methanol at 0 ° C. to precipitate a polymer. This slurry was filtered under reduced pressure and vacuum dried to obtain 2.5 g of the desired product (highly branched polymer 13) as a white powder (yield 36%).
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. Moreover, as for the weight average molecular weight Mw7,700 measured by polystyrene conversion by GPC of a target object, dispersion degree: Mw / Mn was 2.6.

[Example 24] Synthesis of hyperbranched polymer 14 Into a 200 mL reaction flask, 68 g of MIBK was charged, and nitrogen was poured for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 116 ° C).
In another 100 mL reaction flask, DCP 6.7 g (20 mmol), 3FEA 0.3 g (2 mmol), CYM 2.1 g (11 mmol), STA 3.3 g (10 mmol), MAIB 2.8 g (12 mmol) and MIBK 68 g were charged with stirring. Nitrogen was introduced for 5 minutes to replace the nitrogen, and the mixture was stirred under ice cooling (internal temperature 5 ° C.) to dissolve each monomer.
The contents were added dropwise from the 100 mL reaction flask charged with DCP, 3FEA, CYM, STA and MAIB into the refluxed MIBK in the 200 mL reaction flask using a dropping pump over 40 minutes. . After completion of dropping, the mixture was aged for 60 minutes.
Next, 121 g of MIBK was distilled off from this reaction solution using a rotary evaporator, and then dropped into 214 g of methanol at 0 ° C. to precipitate a polymer. This slurry was filtered under reduced pressure and vacuum-dried to obtain 2.9 g of the target product (highly branched polymer 14) as a transparent glassy solid (yield 32%).
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 5,500, and dispersion degree: Mw / Mn was 2.1.

Comparative Example 1 Synthesis of Hyperbranched Polymer 6 To a 200 mL reaction flask, 66 g of toluene was charged, and nitrogen was poured for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 110 ° C.).
Into another 200 mL reaction flask was charged DCP 6.7 g (20 mmol), C6FA 4.2 g (10 mmol), DCHC 3.7 g (12 mmol) and toluene 66 g. And cooled to 0 ° C.
The contents were added dropwise from the 200 mL reaction flask charged with DCP, C6FA, and DCHC to the refluxed toluene in the 200 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, 55 g of toluene was distilled off from the reaction solution using a rotary evaporator, and then added to 510 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 3.8 g of the target product (highly branched polymer 6) as a white powder (yield 27%).
The ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 11 and 12. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 7,200, and dispersion degree: Mw / Mn was 2.9.

[Comparative Example 2] Synthesis of hyperbranched polymer 7 A 200 mL reaction flask was charged with 66 g of toluene, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal solution was refluxed (approximately 110 ° C).
In another 100 mL reaction flask, DCP 6.7 g (20 mmol), C6FA 5.4 g (12.5 mmol), GMA 1.4 g (10 mmol), DCHC 3.7 g (12 mmol) and toluene 66 g were charged, and nitrogen was added for 5 minutes with stirring. Poured with nitrogen, and cooled to 0 ° C. in an ice bath.
The contents were added dropwise from the 100 mL reaction flask charged with DCP, C6FA, GMA, and DCHC to the refluxed toluene in the 200 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, this reaction solution was added to 510 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 6.4 g of the desired product (highly branched polymer 7) as a white powder (yield 40%).
¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 13 and 14. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 8,000, and dispersion degree: Mw / Mn was 1.9.

Charge amount [mol%] (monomer B, monomer type, initiator type, and monomer A) of hyperbranched polymers 1 to 14 obtained in Examples 1 to 5, Examples 18 to 24 and Comparative Examples 1 and 2 Monomer C, polymerization initiator D, monomer E), fluorine monomer (monomer B) introduction amount [mol%] calculated from ¹³ C NMR spectrum, and fluorine atom content [mass%] calculated from fluorine quantitative analysis are shown in Table 1. Shown in

[Evaluation of physical properties of each hyperbranched polymer]
50 mg of each of the hyperbranched polymers 1 to 14 obtained in Examples 1 to 5, Examples 18 to 24 and Comparative Examples 1 and 2 were dissolved in 950 mg of the solvent shown in Table 2 and filtered, and each hyperbranched polymer was filtered. A polymer solution was prepared. This hyperbranched polymer solution was spin-coated on a glass substrate (slope for 5 seconds, then 1,500 rpm for 30 seconds, then further slope for 5 seconds), and heat-treated at 100 ° C. for 30 minutes to evaporate the solvent and form a film.
The refractive index of the obtained thin film at a wavelength of 633 nm and the contact angles of water and diiodomethane were evaluated. The surface energy was calculated from the result of the contact angle. Furthermore, the glass transition temperature (Tg) and 5% weight loss temperature (Td _5% ) of each hyperbranched polymer powder were measured. The obtained results are shown in Table 2.

Example 6 Surface Modification of Epoxy Resin with Hyperbranched Polymer Having Oxetane Structure 50 mg of hyperbranched polymer 1 obtained in Example 1 was added to 5.0 g of CEL2021P and dissolved by heating to approximately 70 ° C. After this mixture was cooled to room temperature (approximately 25 ° C.), 300 mg of CPI-100P was added to prepare an epoxy resin composition.
The obtained epoxy resin composition was poured into a 50 mm square × 1 mm thick silicone mold, with the center portion placed on a release-coated glass substrate cut into 30 mm square. The resin composition in the mold was irradiated with UV light with an exposure amount of 12.5 J / cm ² to produce a cured epoxy resin.
Turbidity (haze value) of the obtained cured product was measured, and transparency was evaluated according to the following criteria. Moreover, the contact angle of water and diiodomethane of the obtained cured product was measured to evaluate liquid repellency. Further, the cured product was immersed in acetone for 1 minute and dried with an air gun, and then the contact angle of water was measured again to evaluate the liquid-repellent organic solvent resistance. The obtained results are shown in Table 3.
[Transparency evaluation criteria]
A: haze value <1
○: 1 ≦ haze value <10
Δ: 10 ≦ haze value <50
×: 50 ≦ haze value

[Examples 7 to 10, 25 to 30] Surface modification of an epoxy resin with a hyperbranched polymer having an alicyclic epoxy group, obtained in Examples 2 to 5 and Examples 18 to 23 in place of the hyperbranched polymer 1 In addition, operations and evaluations were performed in the same manner as in Example 6 except that the hyperbranched polymers 2 to 5 and the hyperbranched polymers 8 to 13 were used. The results are also shown in Table 3.

[Examples 11 and 12] Surface modification of epoxy resin with hyperbranched polymer having alicyclic epoxy group Instead of hyperbranched polymer 1, hyperbranched polymers 3 and 5 obtained in Examples 3 and 5 were used, respectively. Further, the operation and evaluation were conducted in the same manner as in Example 6 except that post-baking was performed at 150 ° C. for 10 minutes after exposure. The results are also shown in Table 3.

[Comparative Example 3] Surface characteristics of epoxy resin without addition of surface modifier The same operation and evaluation as in Example 6 were conducted except that hyperbranched polymer 1 was not added. The results are also shown in Table 3.

[Comparative Example 4] Surface modification of epoxy resin with highly branched polymer having no photocationically polymerizable group Example except that the highly branched polymer 6 obtained in Comparative Example 1 was used instead of the highly branched polymer 1 Operation and evaluation were conducted in the same manner as in 6. The results are also shown in Table 3.

Comparative Example 5 Surface Modification of Epoxy Resin with Highly Branched Polymer Having Epoxy Group The same operation as in Example 6 except that instead of the highly branched polymer 1, the highly branched polymer 7 obtained in Comparative Example 2 was used. ,evaluated. The results are also shown in Table 3.

[Comparative Example 6] Surface characteristics of epoxy resin with no surface modifier added The same operation as in Example 6 except that hyperbranched polymer 1 was not added, and post-baking was performed at 150 ° C for 10 minutes after exposure. ,evaluated. The results are also shown in Table 3.

[Comparative Example 7] Surface modification of epoxy resin with highly branched polymer having no photocationically polymerizable group In place of the highly branched polymer 1, the highly branched polymer 6 obtained in Comparative Example 1 was used. Operations and evaluations were performed in the same manner as in Example 6 except that post-baking was performed at 150 ° C. for 10 minutes. The results are also shown in Table 3.

[Example 13] Surface modification of epoxy resin with hyperbranched polymer having oxetane structure 40 mg of hyperbranched polymer 1 obtained in Example 1 was added to a mixture of 2.0 g of CEL3000 and 2.0 g of GT401 at about 70 ° C. And dissolved by heating. After cooling this mixture to room temperature (approximately 25 ° C.), 240 mg of CPI-100P was added to prepare an epoxy resin composition.
The obtained epoxy resin composition was spin-coated on a glass substrate (200 rpm for 15 seconds, then slope for 15 seconds, 2,000 rpm for 60 seconds, and further for 5 seconds) to obtain a coating film. The entire surface of the coating film was irradiated with UV light having an exposure amount of 6.2 J / cm ² and then post-baked on a hot plate at 120 ° C. for 10 minutes to prepare a cured epoxy resin film.
The turbidity (haze value) of the obtained cured film was measured, and the transparency was evaluated according to the following criteria. Moreover, the water contact angle of the obtained cured film was measured and liquid repellency was evaluated. Further, the cured film was immersed in acetone for 1 minute and dried with an air gun, and then the contact angle of water was measured again to evaluate the liquid-repellent organic solvent resistance. Table 4 shows the obtained results.
[Transparency evaluation criteria]
A: haze value <1
○: 1 ≦ haze value <10
Δ: 10 ≦ haze value <50
×: 50 ≦ haze value

[Examples 14 to 17] Surface modification of epoxy resin with hyperbranched polymer having alicyclic epoxy group Instead of hyperbranched polymer 1, hyperbranched polymers 2 to 5 obtained in Examples 2 to 5 were used, respectively. The operation and evaluation were performed in the same manner as in Example 13 except that. The results are also shown in Table 4.

[Comparative Example 8] Surface characteristics of epoxy resin without addition of surface modifier The same operation and evaluation as in Example 13 were conducted except that hyperbranched polymer 1 was not added. The results are also shown in Table 4.

[Comparative Example 9] Surface modification of epoxy resin with highly branched polymer having no photocationically polymerizable group Example except that the highly branched polymer 6 obtained in Comparative Example 1 was used in place of the highly branched polymer 1 Operation and evaluation were conducted in the same manner as in FIG. The results are also shown in Table 4.

[Comparative Example 10] Surface Modification of Epoxy Resin with Highly Branched Polymer Having Epoxy Group Same operation as in Example 13 except that the highly branched polymer 7 obtained in Comparative Example 2 was used instead of the highly branched polymer 1 ,evaluated. The results are also shown in Table 4.

[Example 31] Preparation of cured epoxy resin to which hyperbranched polymer having oxetane structure was added 40 mg of hyperbranched polymer 1 obtained in Example 1 was added to a mixture of 2.0 g of CEL3000 and 2.0 g of GT401. Heat to 70 ° C. to dissolve. After cooling this mixture to room temperature (approximately 25 ° C.), 240 mg of CPI-100P was added to prepare an epoxy resin composition.
The obtained epoxy resin composition was poured into a 50 mm square × 1 mm thick silicone mold, with the center portion placed on a release-coated glass substrate cut into 30 mm square. The resin composition in the mold was irradiated with UV light having an exposure amount of 6.2 J / cm ² and then post-baked on a hot plate at 120 ° C. for 10 minutes to produce a cured epoxy resin.
Turbidity (haze value) of the obtained cured product was measured, and transparency was evaluated according to the following criteria. The results obtained are shown in Table 5.
[Transparency evaluation criteria]
A: haze value <1
○: 1 ≦ haze value <5
Δ: 5 ≦ haze value <10
×: 10 ≦ haze value

[Examples 32 to 34] Preparation of cured epoxy resin to which a hyperbranched polymer having an alicyclic epoxy group was added In place of the hyperbranched polymer 1, the hyperbranched polymers 2 to 4 obtained in Examples 2 to 4 were used. Operations and evaluations were performed in the same manner as in Example 31 except that each was used. The results are also shown in Table 5.

[Comparative Example 11] Preparation of cured epoxy resin without adding surface modifier The same operation and evaluation as in Example 31 were performed except that the hyperbranched polymer 1 was not added. The results are also shown in Table 5.

[Comparative Example 12] Preparation of cured epoxy resin added with a highly branched polymer having no photocationically polymerizable group Except that the highly branched polymer 6 obtained in Comparative Example 1 was used in place of the highly branched polymer 1 Operations and evaluations were conducted in the same manner as in Example 31. The results are also shown in Table 5.

[Comparative Example 13] Preparation of cured epoxy resin to which a highly branched polymer having an epoxy group was added Similar to Example 31 except that the highly branched polymer 7 obtained in Comparative Example 2 was used instead of the highly branched polymer 1 Was operated and evaluated. The results are also shown in Table 5.

[Example 35] Surface modification of epoxy resin with hyperbranched polymer having alicyclic epoxy group 30 mg of hyperbranched polymer 2 obtained in Example 2 was added to 3.0 g of CEL2021P, and heated to about 70 ° C to dissolve. I let you. After cooling this mixture to room temperature (approximately 25 ° C.), 180 mg of CPI-100P was added to prepare an epoxy resin composition A.
The obtained epoxy resin composition was placed on a glass substrate treated with a release agent (OPTOOL (trademark) DSX [manufactured by Daikin Industries, Ltd.]), and the center part was cut into 30 mm squares, 50 mm squares and 1 mm thick silicones. Another glass substrate which was poured into a mold and not subjected to mold release treatment was covered from above. The resin composition in the mold sandwiched between the two glass substrates was irradiated with UV light with an exposure amount of 12 J / cm ² to produce a cured epoxy resin. After curing, the glass substrate treated with the release agent and the mold were removed, and a surface-modified epoxy resin cured product was obtained.
A drop of separately prepared epoxy resin composition B (CEL2021P100 parts by mass + CPI-100P6 parts by mass) was dropped on the surface of the cured product, and another glass substrate not subjected to mold release treatment was covered from above. The cured product sandwiched between the two glass substrates is exposed to UV light having an exposure amount of 12 J / cm ² and exposed to light through the surface-modified epoxy resin cured product and the cured product of the epoxy resin composition B. Two bonded glass substrates were obtained.
The obtained bonded glass substrate was peeled off by hand, and the releasability of the cured epoxy resin whose surface was modified according to the following criteria was evaluated. Moreover, about what the epoxy resins (surface-modified epoxy resin hardened | cured material and the hardened | cured material of the epoxy resin composition B) peeled, the same operation and evaluation were continued and the durability was confirmed. . The results obtained are shown in Table 6.
[Evaluation criteria for releasability]
◎: The epoxy resins peel off with little force applied ○: When the force is applied, the epoxy resins peel off ×: The epoxy resins do not peel off

[Examples 36 to 39] Surface modification of epoxy resin with hyperbranched polymer having alicyclic epoxy group Hyperbranched polymer 3 obtained in Examples 3, 18, 19 and 21 instead of hyperbranched polymer 2 Operations and evaluations were performed in the same manner as in Example 35 except that 8, 9 and 11 were used. The results are also shown in Table 6.

[Comparative Example 14] Surface characteristics of epoxy resin without addition of surface modifier The same operation and evaluation as in Example 35 were conducted except that hyperbranched polymer 2 was not added. The results are also shown in Table 6.

[Comparative Example 15] Surface Modification of Epoxy Resin with Highly Branched Polymer Having Epoxy Group The same operation as in Example 35 except that the highly branched polymer 7 obtained in Comparative Example 2 was used in place of the highly branched polymer 2 ,evaluated. The results are also shown in Table 6.

Thus, the fluorine-containing highly branched polymer of the present invention had a high contact angle and was excellent in water and diiodomethane liquid repellency. And when the polymer is mixed in a small amount with a cationic photopolymerizable resin such as an epoxy resin to form a cured product, the cured product has excellent transparency and its surface has excellent liquid repellency. In addition, the results showed that the liquid repellency can be kept high even after immersion in acetone. In particular, by post-baking after curing, the liquid repellency after immersion in acetone could be kept higher.
From the above, it was confirmed that the fluorine-containing highly branched polymer of the present invention is very useful as a surface modifier that can easily modify the surface of a photocationically polymerizable resin such as an epoxy resin.

Claims (23)

Monomer A having two or more radical polymerizable double bonds in the molecule, monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule, and an alicyclic epoxy group in the molecule And a monomer C having at least one photocationically polymerizable group and at least one radical polymerizable double bond selected from the group consisting of oxetanyl group and 5 to 200 moles relative to the number of moles of the monomer A A fluorine-containing highly branched polymer obtained by polymerizing in the presence of% amount of a polymerization initiator D , wherein the polymerization initiator D is an azo polymerization initiator . The fluorine-containing highly branched polymer according to claim 1, wherein the monomer A is a compound having either one or both of a vinyl group and a (meth) acryl group. The fluorine-containing highly branched polymer according to claim 2, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound. The fluorine-containing highly branched polymer according to claim 3, wherein the monomer A is an alicyclic di (meth) acrylate. The fluorine-containing highly branched polymer according to claim 4, wherein the monomer A is tricyclodecane dimethanol di (meth) acrylate. The fluorine-containing highly branched polymer according to any one of claims 1 to 5, which is obtained using 5 to 300 mol% of the monomer B with respect to the monomer A. The monomer B is a compound having one or both of a vinyl group or (meth) acrylic group, a fluorine-containing hyperbranched polymer according to any one of claims 1 to 6. The fluorine-containing highly branched polymer according to claim 7, wherein the monomer B is a compound represented by the following formula [1].

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a C 2-12 fluoroalkyl group which may be substituted with a hydroxy group.) The fluorine-containing highly branched polymer according to claim 8, wherein the monomer B is a compound represented by the following formula [2].

(Wherein R ¹ represents the same meaning as defined in Formula [1], X represents a hydrogen atom or a fluorine atom, m represents 1 or 2, and n represents an integer of 0 to 5). The fluorine-containing highly branched polymer according to any one of claims 1 to 9, which is obtained using 10 to 300 mol% of the monomer C with respect to the monomer A. Wherein monomer C is a compound having one or both of a vinyl group or (meth) acrylic group, a fluorine-containing hyperbranched polymer according to any one of claims 1 to 10. The fluorine-containing highly branched polymer according to claim 11, wherein the monomer C is a compound represented by the following formula [3].

(In the formula, R ³ represents a hydrogen atom or a methyl group, and L represents a single bond, or an alkylene group having 1 to 6 carbon atoms which may contain an ether bond or an ester bond.) The fluorine-containing highly branched polymer according to claim 11, wherein the monomer C is a compound represented by the following formula [4].

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and L may include a single bond, an ether bond or an ester bond. Represents an alkylene group having 1 to 6 carbon atoms.) The fluorine-containing highly branched polymer according to any one of claims 1 to 13, wherein the polymerization initiator D is dimethyl 1,1'-azobis (1-cyclohexanecarboxylate). Furthermore, any one of Claims 1 thru | or 14 obtained by copolymerizing the monomer E represented by following formula [5] of 5-300 mol% quantity with respect to the number-of-moles of the said monomer A. The fluorine-containing highly branched polymer according to item .

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 6 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.) A surface modifier for a cationic photopolymerizable resin, comprising the fluorine-containing highly branched polymer according to any one of claims 1 to 15 . A photocationically polymerizable resin composition comprising (a) the fluorine-containing highly branched polymer according to any one of claims 1 to 15 and (b) a photocationically polymerizable resin prepolymer. The resin composition of Claim 17 containing 0.001 thru | or 20 mass% of said (a) fluorine-containing hyperbranched polymer with respect to the mass of said (b) prepolymer. The resin composition according to claim 17 or 18 , wherein the (b) prepolymer is a compound having at least one alicyclic epoxy group. The resin composition according to any one of claims 17 to 19, further comprising (c) a photoacid generator. The resin composition according to claim 20 , comprising 0.05 to 30% by mass of the (c) photoacid generator based on the mass of the (b) prepolymer. A cured product obtained from the resin composition according to any one of claims 17 to 21 . Monomer A having two or more radical polymerizable double bonds in the molecule, monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule, and an alicyclic epoxy group in the molecule And a monomer C having at least one photocationically polymerizable group and at least one radical polymerizable double bond selected from the group consisting of oxetanyl group and 5 to 200 moles relative to the number of moles of the monomer A method for producing a% amount of the polymerization initiator is characterized in that the polymerization in the presence of D, the polymerization initiator D is Ru azo polymerization initiators der, fluorine-containing hyperbranched polymers.

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