JP2012251035A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition with which a high hardness cured product (coating film) having excellent transparency and water repellency is obtained.SOLUTION: The curable resin composition comprises a fluorine atom-free compound (A) having ≥6 (meth)acryloyloxy groups per molecule, a silsesquioxane (B) having a fluoroalkyl group and a reactive functional group capable of reacting with the (meth)acryloyloxy group, and a photopolymerization initiator (C).

Description

  The present invention relates to a curable resin composition.

  Plastic molded products such as glass and polycarbonate resin are generally coated with a coating film (also called “top coat”, “hard coat”, etc.) from the viewpoint of protecting the surface from damage, etc. Various things are known as curable resin composition used in order to obtain a coating film.

For example, Patent Document 1 describes “(meth) acrylate polymer (A), (meth) acryloyloxy group-containing silicone resin (B), photocurable resin (C) and photopolymerization initiator (D). Contains ... a curable resin composition in which the photocurable resin (C) has 6 to 15 (meth) acryloyloxy groups in one molecule ([Claim 1]), and "... total mass." In contrast, the content of the curable resin (C) is 60 to 80% by mass ([Claim 6]).
According to the curable resin composition described in Patent Document 1, it is said that “a top coat layer excellent in wear resistance and adhesion can be formed” ([0013]).

JP 2011-016871 A

  In recent years, the level of properties required for a curable resin composition has further increased. For example, a coating film (hard coat) for covering a headlamp of an automobile or a touch panel of a mobile phone has a high hardness and an excellent property. Transparency and water repellency are required.

  Therefore, an object of the present invention is to provide a curable resin composition that can obtain a cured product (coating film) having high hardness and excellent transparency and water repellency.

As a result of intensive studies to achieve the above object, the present inventor has blended a predetermined silsesquioxane into the curable resin composition, so that the resulting coating film has high hardness, and has transparency and water repellency. The present invention was completed.
That is, the present invention provides the following (1) to (4).

  (1) A compound having no fluorine atom (A) having 6 or more (meth) acryloyloxy groups in one molecule, a reactive functional group capable of reacting with the (meth) acryloyloxy group, and fluoro A curable resin composition comprising a silsesquioxane (B) having an alkyl group and a photopolymerization initiator (C).

  (2) The curable resin composition according to (1), wherein the compound (A) has an isocyanurate ring.

  (3) The (1) or (2), wherein the reactive functional group is at least one selected from the group consisting of a (meth) acryloyloxy group, an amino group, a mercapto group, an isocyanate group, and a hydroxyimino group. ) Curable resin composition.

  (4) The content of the silsesquioxane (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the compound (A), and the content of the photopolymerization initiator (C) is Curable resin composition in any one of said (1)-(3) which is 1-20 mass parts with respect to 100 mass parts of said compounds (A).

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which is high hardness and can obtain the hardened | cured material (coating film) excellent in transparency and water repellency can be provided.

[Curable resin composition]
The curable resin composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) is a compound having no fluorine atom and having 6 or more (meth) acryloyloxy groups in one molecule (A ), A silsesquioxane (B) having a reactive functional group capable of reacting with the (meth) acryloyloxy group, and a fluoroalkyl group, and a photopolymerization initiator (C). It is a resin composition.
Hereinafter, each component contained in the composition of the present invention will be described in detail.

[Compound (A)]
The compound (A) contained in the composition of the present invention is not particularly limited as long as it does not have a fluorine atom and has 6 or more (meth) acryloyloxy groups in one molecule.

The “(meth) acryloyloxy group” means an acryloyloxy group (CH ₂ ═CHCOO—) and / or a methacryloyloxy group (CH ₂ ═C (CH ₃ ) COO—).
By containing the compound (A), the composition of the present invention is excellent in coatability (leveling property) and curability, and the resulting coating film (cured product) has higher hardness and adhesion to the substrate. It will be good.

  The number of (meth) acryloyloxy groups contained in one molecule of the compound (A) is preferably 6 to 15 because a coating film having higher hardness can be obtained.

  Examples of such a compound (A) include urethane (meth) acrylate (A1) and silsesquioxane (A2) described below.

<Urethane (meth) acrylate (A1)>
The urethane (meth) acrylate (A1) is a urethane (meth) acrylate having no fluorine atom and having a urethane bond and 6 or more (meth) acryloyloxy groups in one molecule. “Urethane (meth) acrylate” means urethane acrylate and / or urethane methacrylate.

As such urethane (meth) acrylate (A1), polyisocyanate (a11) having two or more isocyanate groups in one molecule, one or more hydroxy groups and six or more (meta) in one molecule. It is preferably a urethane (meth) acrylate obtained by reacting the compound (a12) having an acryloyloxy group.
Below, polyisocyanate (a11) and a compound (a12) are demonstrated.

(Polyisocyanate (a11))
Examples of the polyisocyanate (a11) include aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone Cycloaliphatic polyisocyanates such as diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H ₆ XDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI); TDI (eg 2,4-tolylene diisocyanate (2,4-TDI) ), 2,6-tolylene diisocyanate (2,6-TDI)), MDI (for example, 4,4'-diphenylmethane diisocyanate (4,4'-M DI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine Aromatic polyisocyanates such as diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; these isocyanurates; and the like, and these may be used alone. More than one species may be used in combination.
Among these, from the viewpoint of the hardness of the coating film (cured product) obtained from the composition of the present invention, an isocyanurate body is preferable, an isocyanurate body of aliphatic polyisocyanate or alicyclic polyisocyanate is more preferable, HDI or An isocyanurate form of IPDI is more preferable.

(Compound (a12))
Examples of the compound (a12) include 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the skeleton is pentaerythritol. A certain compound, a compound whose skeleton is dipentaerythritol, and the like may be mentioned, and these may be used alone or in combination of two or more.
Examples of the compound whose skeleton is pentaerythritol include pentaerythritol tri (meth) acrylate.
Examples of the compound whose skeleton is dipentaerythritol include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.
Of these, pentaerythritol triacrylate (PETIA), dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate (DPPA) are preferable.

(Production of urethane (meth) acrylate (A1))
In manufacture of urethane (meth) acrylate (A1), it is preferable that the quantity of a compound (a12) is 1.5-2.5 mol with respect to 1 mol of polyisocyanate (a11).
As a method for producing urethane (meth) acrylate (A1), for example, polyisocyanate (a11) and compound (a12) can be used as an existing organotin catalyst (for example, dibutyltin dilaurate) as a catalyst under the conditions of 50 to 80 ° C. And a method using methyl ethyl ketone and ethyl acetate as a solvent.

  As such urethane (meth) acrylate (A1), those having 6 to 15 (meth) acryloyloxy groups in one molecule are preferable from the viewpoint of hardness of the resulting coating film, and specifically, Examples thereof include those represented by the following formula (A1-1), the following formula (A1-2), and the following formula (A1-3).

<Silsesquioxane (A2)>
The silsesquioxane (A2) is a silsesquioxane having no fluorine atom and having 6 or more (meth) acryloyloxy groups in one molecule. If such a silsesquioxane is used, There is no particular limitation.
Although “silsesquioxane” is described in detail later, it is a general term for polysiloxanes whose basic structural units are T units, and is known to have structures such as a random structure, a cage structure, and a ladder structure. Yes.

  As such silsesquioxane (A2), a commercially available product can be used, and specific examples thereof include “AC-SQ SI-, which is a silsesquioxane having an acryloyloxy group (acryloxypropyl group). 20 "(manufactured by Toagosei Co., Ltd.).

[Silsesquioxane (B)]
The silsesquioxane (B) contained in the composition of the present invention is a reactive functional group (hereinafter simply referred to as “reactive functional group”) that can react with the (meth) acryloyloxy group of the compound (A). And a silsesquioxane having a fluoroalkyl group.

<General description of silsesquioxane>
First, general “silsesquioxane” will be described.
A silicon-containing polymer whose main chain is composed of siloxane bonds (Si—O—Si bonds) is referred to as “polysiloxane”. Since the silicon atom has four bonds, as the basic structural unit of polysiloxane, there are four types of M units, D units, T units, and Q units as shown in the following formula (R is Represents an organic group).

“Silsesquioxane” is a general term for polysiloxanes whose basic structural units are T units. In silsesquioxane, since a silicon atom is bonded to three oxygen atoms and an oxygen atom is bonded to two silicon atoms, silsesquioxane is referred to as “(RSiO _3/2 ) _n ”. (R represents an organic group, and n represents an integer).

As a structure of a siloxane bond skeleton in silsesquioxane, a random structure, a ladder structure, and a cage structure are known.
Here, the cage structure is a structure in which the volume is determined by a plurality of rings formed by covalently bonded atoms, and points located within the volume cannot be separated from the volume without passing through the ring.
The silsesquioxane having a cage structure is a silsesquioxane in which each unit (RSiO _3/2 ) is linked by sharing an oxygen atom, specifically, For example, a silsesquioxane represented by the following formula (B-1) in which n in the above formula is 8, and a silsesquioxane represented by the following formula (B-2) in which n in the above formula is 10. Oxane, silsesquioxane represented by the following formula (B-3) in which n in the above formula is 12, and the like.

<Description of Silsesquioxane (B) in the Present Invention>
The silsesquioxane (B) in the present invention is not particularly limited as long as it is a silsesquioxane as described above and has a reactive functional group and a fluoroalkyl group.

The composition of the present invention has higher hardness due to the siloxane bond skeleton of silsesquioxane (B).
Moreover, in the composition of this invention, silsesquioxane (B) is excellent in the dispersibility with respect to the compound (A) mentioned above by having a reactive functional group, and, thereby, the transparency of the coating film obtained is excellent. It is considered excellent.
Furthermore, in the coating film obtained from the composition of the present invention, it is considered that fluorine atoms derived from the fluoroalkyl group of silsesquioxane (B) are arranged on the surface and have excellent water repellency.
At this time, the reactive functional group of the silsesquioxane (B) partially reacts (bonds) with the (meth) acryloyloxy group of the compound (A) and does not react with the (meth) acryloyloxy group. It is considered that the fluoroalkyl group of oxane (B) appears and is arranged on the surface of the coating film with the driving force that air is hydrophobic.

  The reactive functional group possessed by silsesquioxane (B) is not particularly limited as long as it is a group capable of reacting with (meth) acryloyloxy group (reactable). For example, (meth) acryloyloxy group, amino Group, mercapto group, isocyanate group, hydroxyimino group and the like. Among them, from the viewpoint of reactivity with (meth) acryloyloxy group, (meth) acryloyloxy group, amino group and mercapto group are preferable. .

The fluoroalkyl group possessed by silsesquioxane (B) refers to a group in which some or all of the hydrogen atoms in the alkyl group are substituted with fluorine atoms. A fluoroalkyl group, and a perfluoroalkyl group having 1 to 6 carbon atoms is preferred, and specific examples thereof include a trifluoromethyl group (CF _3- ), a pentafluoroethyl group (C ₂ F _5- ), heptafluoropropyl group (C ₃ F ₇ -), tridecafluorohexyl group _{(C 6 F 13 -),} CF 3 - (CF 2) x - (CH 2) y - group (wherein, x indicated by the An odd number such as 3, 5, 7, 9, etc., and y represents an integer of 0, 1, 2, 3, etc.), (CF ₃ ) ₂ —CF— (CF ₂ ) _x — (CH ₂ ) _y — A group shown (wherein x represents an even number such as 4, 6, 8, etc., y represents 0, 1, 2, 3, etc.) A group represented by CF ₃ (CF ₂ ) _x —R— (CH ₂ ) _y — (wherein x represents an integer of 0 or more, y represents 0, 1, 2, 3, etc.) Represents an integer, and R represents a divalent group such as —C ₆ H ₄ — or —C (═O) —NH—).

Moreover, as a fluoroalkyl group which silsesquioxane (B) has, the group obtained using various reaction may be sufficient, for example, by reaction represented by following formula (i), (ii), etc. Examples include groups obtained (Si in each formula represents a silicon atom of silsesquioxane).
_{-Si- (CH 2) 3 -NCO +} OH- (CH 2) 3 - (CF 2) 4 -H (i)
_{-Si- (CH 2) 3 -SH +} H- (CF 2) 4 - (CH 2) 2 -O-C (= O) -CH = CH 2 (ii)

Of these, a tridecafluorohexyl group (C ₆ F ₁₃ —) is preferable from the viewpoint of the superior water repellency of the resulting coating film and safety.

Such silsesquioxane (B) can be represented by, for example, the following formula (1).
_{^{(R 1 -X-SiO 3/2)}} n (1)

In the above formula (1), n represents an integer of 6 or more, X represents a single bond or an alkylene group, and R ¹ represents a reactive functional group or a fluoroalkyl group. A plurality of R ¹ may be the same or different, but at least one R ¹ represents a reactive functional group, and another R ¹ represents a fluoroalkyl group.

  The integer of 6 or more represented by n in the above formula (1) is preferably 6-20.

  Examples of the alkylene group represented by X in the above formula (1) include an alkylene group having 1 to 6 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, propane-1,3- Examples include a diyl group, a butane-1,4-diyl group, a heptane-1,5-diyl group, and a hexane-1,6-diyl group, and among them, an ethylene group and a propane-1,3-diyl group. Is preferred.

Examples of the silsesquioxane (B) represented by the above formula (1) include a silsesquioxane having a cage structure in which n in the above formula (1) represents 8. Specifically, for example, What is represented by Formula (2) is mentioned. In the following formula (2), X and R ¹ has the same meaning as X and R ¹ in the formula (1).

As a method for producing such a silsesquioxane (B), for example, a method obtained by hydrolytic condensation of a trialkoxysilane (silane coupling agent) having a predetermined functional group, that is, the reactive functional group described above And a method of hydrolyzing and condensing the trialkoxysilane (b1) having the above and the trialkoxysilane (b2) having the fluoroalkyl group described above.
In this case, more specifically, for example, trialkoxysilane (b1) and trialkoxysilane (b2) are charged into the reaction system at a predetermined charge amount, and a solvent such as an aqueous tetramethylammonium hydroxide solution is gradually added. Then, the system is stirred at room temperature for hydrolysis and condensation, and after completion of the stirring, the solvent is distilled off to obtain silsesquioxane (B).

  The alkoxy group possessed by the trialkoxysilane (b1) and the trialkoxysilane (b2) is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. An ethoxy group is preferred.

  The charge amount (mol) of trialkoxysilane (b1) and trialkoxysilane (b2) is not particularly limited, and the molar ratio (b1 / b2) as the charge amount ratio is, for example, 1/7 to 7 / However, from the viewpoint that the water repellency of the coating film obtained from the composition of the present invention is more excellent, the latter amount is preferably larger, more preferably 1/7 to 3/5. preferable.

As the trialkoxysilane (b1), a commercially available product can be used. Specific examples thereof include 3-acryloxypropyltrimethoxysilane [(CH ₃ O) ₃ SiC ₃ H ₆ OOCHC = having an acryloyloxy group. CH ₂ ] (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ SiC ₃ H ₆ SH] (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) having a mercapto group ), Γ-aminopropyltrimethoxysilane [(CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ ] (KBM-903, Shin-Etsu Chemical Co., Ltd.) having an amino group.

As the trialkoxysilane (b2), it may be a commercial product, and specific examples thereof include trifluoropropyl trimethoxysilane _{[(CH 3 O) 3 SiC} 2 H 4 CF 3] (KBM-7103, Manufactured by Shin-Etsu Chemical Co., Ltd.), triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane [(CH ₃ O) ₃ SiC ₂ H ₄ C ₆ F ₁₃ ] (Dynasylan F8261, manufactured by Evonik Degussa) Etc.

  The content of silsesquioxane (B) thus obtained is 0.1% with respect to 100 parts by mass of the compound (A) described above, because the transparency and water repellency of the resulting coating film are more excellent. It is preferably 10 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass.

[Photopolymerization initiator (C)]
The photopolymerization initiator (C) contained in the composition of the present invention is not particularly limited as long as it can polymerize, for example, a compound having a radical polymerizable functional group by light.

  Examples of the photopolymerization initiator (C) include alkylphenone photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylchuram monosulfide, benzoins, and benzoin methyl ether. Thioxanthones, propiophenones, benzyls, and acylphosphine oxides. These may be used alone or in combination of two or more.

Of these, alkylphenone photopolymerization initiators are preferred from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility with resins, low volatility, and low odor.
Specific examples of the alkylphenone photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like are mentioned, among which 1-hydroxy-cyclohexyl-phenyl-ketone is preferable.
A commercially available product can be used as 1-hydroxy-cyclohexyl-phenyl-ketone, and specific examples include Irgacure 184 (manufactured by BASF).

  Content of a photoinitiator (C) is 1-20 mass with respect to 100 mass parts of compounds (A) mentioned above from the reason that sclerosis | hardenability of the composition of this invention is excellent and a favorable coating film is obtained. Part is preferable, and 2 to 10 parts by mass is more preferable.

[Other ingredients]
(solvent)
The composition of the present invention may contain a solvent from the viewpoint of workability and the like. The solvent is an organic solvent, for example, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, dodecylbenzene and methylnaphthalene; methylene chloride, chloroform , Ethylene chloride, chlorobenzene, etc .; THF, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, and other ethers; ethyl acetate, butyl acetate, butyl acrylate, methyl methacrylate, hexamethylene diacrylate , Esters such as trimethylolpropane triacrylate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; propylene Examples include glycol ethers such as recall monomethyl ether, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve; alcohols such as isopropyl alcohol, and the like. These may be used alone or in combination. You may use the above together.

(Additive)
The composition of the present invention is an additive such as a filler, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesiveness imparting agent, a leveling agent, and a dispersant as long as the object of the present invention is not impaired. , Antifoaming agents, matting agents, light stabilizers (for example, hindered amine compounds), dyes, pigments and the like.

  The method for producing the composition of the present invention is not particularly limited. For example, the composition is produced by a method in which the above-described essential components and optional components are placed in a reaction vessel and sufficiently kneaded using a stirrer such as a mixing mixer under reduced pressure. can do.

  The composition of this invention can be used for the use which coat | covers the surface of a glass substrate or a plastic base material, for example, can be used as a composition for hard-coats.

The glass substrate is not particularly limited, and various glass substrates can be used.
As the plastic substrate, various plastic substrates can be used regardless of thermoplastic plastics and thermosetting plastics. Specifically, for example, polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer are used. Polymerized resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin and the like can be mentioned, and polycarbonate resin is preferable.

The method for applying the composition of the present invention is not particularly limited, and for example, known application methods such as brush coating, flow coating, dip coating, spray coating, and spin coating can be employed.
In addition, as an application quantity of the composition of this invention, it is preferable to make it the film thickness of the coating film at the time of hardening become 1-30 micrometers.

The composition of the present invention can be cured by ultraviolet rays. The irradiation amount of the ultraviolet rays used when the composition of the present invention is cured is preferably 500 to 3000 mJ / cm ² from the viewpoint of fast curability and workability. The temperature for curing the composition of the present invention by ultraviolet irradiation is preferably 20 to 100 ° C. The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

[Production of component (B)]
First, the component (B) used in each Example and Comparative Example to be described later was produced.

[SQ AC / F3 (1/7)]
First, 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter the same) and trifluoropropyltrimethoxysilane (KBM-7103, manufactured by Shin-Etsu Chemical Co., Ltd., the same applies below) 1 : The reaction system was charged at a molar ratio of 7.
Specifically, 5.37 g of 3-acryloxypropyltrimethoxysilane and 34.4 g of trifluoropropyltrimethoxysilane were charged into the reaction system. Then, after dissolving in about 200 g of tetrahydrofuran (THF) solvent and stirring the system, 5.11 g of 5.1% tetramethylammonium hydroxide aqueous solution was gradually added, and the system was stirred at room temperature for 24 hours. And then hydrolytically condensed.
After stirring, about 200 g of butyl acetate was added to the system, and the reaction solution was washed with a saturated sodium chloride / potassium chloride aqueous solution using a separatory funnel. Washing with water was repeated until the aqueous layer in the separating funnel became neutral, and then the organic layer was separated and dehydrated with anhydrous magnesium sulfate.
Thereafter, a solvent such as butyl acetate is distilled off under reduced pressure, whereby silsesquioxane (“SQ”) having an acryloyloxy group and a trifluoromethyl group (CF ₃ —) in a ratio of 1: 7 in one molecule. AC / F3 (1/7) ", and so on). The silsesquioxane includes a silsesquioxane having a cage structure represented by the following formula (3).

The obtained product was subjected to ¹ H-NMR and ¹³ C-NMR analyses, and as a result, disappearance of a signal attributable to the —OCH ₃ group observed near 3.75 ppm and 50 ppm was confirmed. It was. Further, as a result of IR measurement, absorption derived from Si—O—Si bond was observed in the vicinity of 1110 cm ⁻¹ .
Such a result was the same also about all the products described below manufactured as a component (B).

[SQ AC / F3 (2/6)]
3-acryloxypropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as above except that the reaction system was charged at a molar ratio of 2: 6, and acryloyloxy group was contained in one molecule. And a silsesquioxane having a trifluoromethyl group (CF ₃ —) in a ratio of 2: 6 was obtained.

[SQ AC / F3 (3/5)]
3-acryloxypropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as described above except that the reaction system was charged at a molar ratio of 3: 5 to give an acryloyloxy group in one molecule. Silsesquioxane having a trifluoromethyl group (CF ₃ —) ratio of 3: 5 was obtained.

[SQ AC / F3 (4/4)]
3-acryloxypropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as described above except that the reaction system was charged in a molar ratio of 4: 4 to give an acryloyloxy group in one molecule. And a silsesquioxane having a trifluoromethyl group (CF ₃ —) in a ratio of 4: 4 was obtained.

[SQ AC / F3 (6/2)]
3-acryloxypropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as above except that the reaction system was charged in a molar ratio of 6: 2, and acryloyloxy group was contained in one molecule. And a silsesquioxane having a trifluoromethyl group (CF ₃ —) in a ratio of 6: 2.

[SQ AC / F3 (7/1)]
3-acryloxypropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as above except that 7: 1 molar ratio was charged into the reaction system, and acryloyloxy group in one molecule. And silsesquioxane having a trifluoromethyl group (CF ₃ —) in a ratio of 7: 1 were obtained.

[SQ AC / F13 (1/7)]
3-acryloxypropyltrimethoxysilane and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane (Dynasylan F8261, manufactured by Evonik Degussa, the same applies hereinafter) at a molar ratio of 1: 7. except that charged to the reaction system by hydrolytic condensation in the same manner as described above, acryloyloxy group and tridecafluorohexyl groups in a molecule (C ₆ F ₁₃ -) and a 1: 7 silsesquioxane having a ratio of Got. The silsesquioxane includes a silsesquioxane having a cage structure represented by the following formula (4).

[SQ AC / F13 (4/4)]
Except that 3-acryloxypropyltrimethoxysilane and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane were charged into the reaction system at a molar ratio of 4: 4, the same as above. A silsesquioxane having an acryloyloxy group and a tridecafluorohexyl group (C ₆ F ₁₃ —) in a ratio of 4: 4 in one molecule was obtained.

[SQ AC / F13 (6/2)]
Hydrolysis was performed in the same manner as above except that 3-acryloxypropyltrimethoxysilane and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane were charged into the reaction system at a molar ratio of 6: 2. is engaged decomposition condensation, acryloyloxy group and tridecafluorohexyl groups per molecule - a ₆ (C 6 F _13): to obtain a silsesquioxane having 2 at a rate.

[SQ AC / F13 (7/1)]
Hydrolysis condensation was carried out in the same manner as above except that 7 mol of 3-acryloxypropyltrimethoxysilane and 1 mol of triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane were charged into the reaction system. , acryloyloxy group and tridecafluorohexyl groups in a molecule (C ₆ F ₁₃ -) and a 7: to obtain a silsesquioxane having a ratio of 1.

[SQ NH2 / F3 (1/7)]
Hydrolysis similar to the above except that γ-aminopropyltrimethoxysilane (KBM-903, Shin-Etsu Chemical Co., Ltd.) and trifluoropropyltrimethoxysilane were charged into the reaction system at a molar ratio of 1: 7. By condensation, a silsesquioxane having an amino group and a trifluoromethyl group (CF ₃ —) in a ratio of 1: 7 in one molecule was obtained. The silsesquioxane includes a silsesquioxane having a cage structure represented by the following formula (5).

[SQ SH / F3 (1/7)]
γ-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd., the same applies below) and trifluoropropyltrimethoxysilane in the molar ratio of 1: 7 were charged into the reaction system in the same manner as described above. Hydrolysis condensation was performed to obtain silsesquioxane having a mercapto group and a trifluoromethyl group (CF ₃ —) in a ratio of 1: 7 in one molecule. The silsesquioxane includes a silsesquioxane having a cage structure represented by the following formula (6).

[SQ SH / F3 (2/6)]
γ-mercaptopropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as described above except that the reaction system was charged at a molar ratio of 2: 6. A silsesquioxane having a fluoromethyl group (CF ₃ —) in a ratio of 2: 6 was obtained.

[SQ SH / F3 (3/5)]
γ-mercaptopropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as described above except that the reaction system was charged at a molar ratio of 3: 5. Silsesquioxane having a fluoromethyl group (CF ₃ —) in a ratio of 3: 5 was obtained.

[SQ SH / F3 (6/2)]
γ-mercaptopropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as described above except that the reaction system was charged in a molar ratio of 6: 2, and mercapto groups and trimethylsilane were combined in one molecule. Silsesquioxane having a fluoromethyl group (CF ₃ —) in a ratio of 6: 2 was obtained.

[SQ SH / F3 (7/1)]
γ-mercaptopropyltrimethoxysilane and trifluoropropyltrimethoxysilane were hydrolyzed and condensed in the same manner as described above except that the reaction system was charged in a molar ratio of 7: 1. Silsesquioxane having a fluoromethyl group (CF ₃ —) in a ratio of 7: 1 was obtained.

[SQ AC]
It was hydrolyzed and condensed in the same manner as described above except that only 42.1 g of 3-acryloxypropyltrimethoxysilane was charged into the reaction system, and had only an acryloyloxy group and had a fluoroalkyl group such as a trifluoromethyl group. No silsesquioxane was obtained.

[SQ SH]
Silyl which is hydrolyzed and condensed in the same manner as described above except that only 35.4 g of γ-mercaptopropyltrimethoxysilane is charged into the reaction system, has only a mercapto group, and does not have a fluoroalkyl group such as a trifluoromethyl group. Sesquioxane was obtained.

[SQ F3]
Except that only 39.3 g of trifluoropropyltrimethoxysilane was charged into the reaction system, it was hydrolyzed and condensed in the same manner as described above to have only a trifluoromethyl group (CF _3- ), and an acryloyloxy group, amino group, mercapto Silsesquioxane having no reactive functional group such as a group was obtained.

<Examples 1-16, Comparative Examples 1-8>
The components shown in the following Table 1 (unit: parts by mass), and the components shown in the table are mixed with a solvent (isopropyl alcohol: 30% by mass, butyl acetate: 30% by mass, propylene glycol monomethyl ether: 20% by mass, diisobutyl (Ketone: mixed solvent of 20% by mass) and mixed using a stirrer to obtain each curable resin composition.

<Evaluation>
Each obtained curable resin composition was apply | coated to the polycarbonate substrate using the spray so that it might become a film thickness of 10-30 micrometers. Then, after oven drying (70 ° C., 3 minutes), UV irradiation is performed using a GS UV SYSTEM manufactured by Kawaguchi Spring Mfg. Co., Ltd. so that the peak intensity is 80 mW / cm ² and the integrated light intensity is 1000 mJ / cm ² A coating film was formed to obtain an evaluation sample.
Each characteristic was evaluated by the following method using this sample for evaluation.

(Transparency / total light transmittance)
The total light transmittance [%] of the sample for evaluation was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.). When the total light transmittance is 85% or more, the transparency is evaluated as “◯” because it is excellent in transparency and practical, and when the total light transmittance is less than 85%, the transparency is inferior. The transparency was evaluated as “×”.
The evaluation results of transparency and the values of total light transmittance are shown in Table 1 below.

(Water contact angle)
A 10 μm ³ water droplet is dropped at a rate of 2 μm ³ / sec on the coating film surface of the evaluation sample installed horizontally, and a water contact angle (°) using a contact angle measuring device (OCA20, manufactured by Data Physics). Was measured. The average water contact angle for 5 drops (right and left) is shown in Table 1 below. At this time, when the water contact angle is 80 ° or more, the water repellency is excellent.

(Abrasion resistance)
The coating surface of the sample for evaluation was rubbed with steel wool (# 0000) at a load of 250 g / cm ² until scratches could be visually confirmed in 10 reciprocation increments, and scratch resistance was evaluated by the number of reciprocations. . The number of round trips is shown in Table 1 below. If the number of reciprocations is 200 or more, it can be evaluated that the hardness is high.

The other components shown in Table 1 are as follows.
15 functional acrylate: 15 functional acrylate represented by the above formula (A1-3) obtained by reacting dipentaerythritol pentaacrylate with an isocyanurate of isophorone diisocyanate.
Multifunctional silsesquioxane: AC-SQ SI-20 (manufactured by Toagosei Co., Ltd.)
-5-functional acrylate: dipentaerythritol pentaacrylate (M-403, manufactured by Toagosei Co., Ltd.)
Teflon (registered trademark): polytetrafluoroethylene (manufactured by DuPont)
Photoinitiator: Irgacure 184 (manufactured by BASF)

From the results shown in Table 1 above, it was found that Examples 1 to 16 were all excellent in transparency and water repellency and had high hardness.
In particular, Examples 1 to 14 using a 15-functional acrylate as the component (A) were higher in hardness than Examples 15 and 16 using a polyfunctional silsesquioxane.
Moreover, Examples 12 to 14 using SQ AC / F13 having a tridecafluorohexyl group (C ₆ F ₁₃ —) as the component (B) have a large water contact angle and tend to be more excellent in water repellency. I understood.

On the other hand, it was found that Comparative Examples 1 and 5 not using the component (B) had a small water contact angle and poor water repellency.
It was also found that Comparative Examples 2 and 3 using the component (B) having no fluoroalkyl group also had a small contact angle and poor water repellency.
Moreover, it turned out that the comparative example 4 using the component (B) which has only a fluoroalkyl group is inferior to transparency.
Moreover, it turned out that the comparative example 6 which uses pentafunctional acrylate as a component (A) is inferior to abrasion resistance, and cannot obtain high hardness.
Moreover, the comparative example 7 which does not use a component (A) did not harden | cure a coating film but could not evaluate each characteristic (it shows by "-" in the said Table 1).
Moreover, although the comparative example 8 using Teflon (trademark) as a component (B) was excellent in water repellency, it turned out that it is inferior to transparency.

Claims (4)

A compound (A) having no fluorine atom and having 6 or more (meth) acryloyloxy groups in one molecule;
Silsesquioxane (B) having a reactive functional group capable of reacting with the (meth) acryloyloxy group and a fluoroalkyl group,
A photopolymerization initiator (C);
A curable resin composition containing   The curable resin composition according to claim 1, wherein the compound (A) has an isocyanurate ring.   The curable property according to claim 1 or 2, wherein the reactive functional group is at least one selected from the group consisting of a (meth) acryloyloxy group, an amino group, a mercapto group, an isocyanate group, and a hydroxyimino group. Resin composition. Content of the said silsesquioxane (B) is 0.1-10 mass parts with respect to 100 mass parts of said compounds (A),
Curable resin composition in any one of Claims 1-3 whose content of the said photoinitiator (C) is 1-20 mass parts with respect to 100 mass parts of said compounds (A).