JPH0811777B2 - Low refractive index resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition that can be cured by irradiation with active energy rays such as electron beams or ultraviolet rays, and more specifically,
The present invention relates to an active energy ray-curable resin composition which gives a strong and transparent cured resin having a low refractive index upon irradiation with active energy rays.

Fluorine-containing polymers generally have high chemical resistance, weather resistance,
Since it has water and oil repellency and surface lubricity, it has been used as a highly functional material in various fields. In recent years, however, its optical property, that is, a low refractive index has attracted attention, and it is used as a sheath material for optical transmission fibers. The use as a low reflective coating has been activated.

The optical transmission fiber is roughly classified into an inorganic glass type and a synthetic resin type, and each of them is composed of a highly transparent core portion having a high refractive index and a sheath portion having a relatively small refractive index. Conventionally, as a method of forming a sheath portion, coating with a silicone compound or a fluorine-containing polymer having a low refractive index has been proposed and carried out. For example, (1) a method of applying a silicone-based resin composition to a drawn quartz-based core wire and forming a sheath portion of the silicone resin by thermosetting,
(2) Poly (methyl methacrylate) or poly (styrene) which is a core material, and a fluorinated alkyl group-containing (meth) acrylate obtained by a polymerization method such as solution polymerization, bulk polymerization or emulsion polymerization. Coalescence, copolymer of fluorinated alkyl group-containing (meth) acrylate with other comonomers, or poly (tetrafluoroethylene), poly (vinylidene fluoride / tetrafluoroethylene), poly (vinylidene fluoride / hexafluoropropylene) ) And other fluoropolymers to form a sheath portion comprising the fluoropolymer (Japanese Patent Publication No. 43-8978 and Japanese Patent Publication No. 56-
No. 8321, Japanese Patent Publication No. 56-8322, Japanese Patent Publication No. 56-8323,
59-84203, JP-A-59-84204, JP-A-59-98116
No. 59, JP-A-147011, JP-A-59-204002),
(3) A quartz-type or plastic-type core wire formed into a fibrous shape is coated with a melt or solution of a fluorine-containing polymer such as poly (vinylidene fluoride / tetrafluoroethylene) to form a sheath portion. There are proposals such as methods (Japanese Patent Publication No. 53-21660 and Japanese Patent Publication No. 56-41966).

However, among these proposals, the silicone resin described in (1) has excellent heat resistance, but is poor in oil resistance, and has a drawback that it swells when immersed in mineral oil and causes a change in refractive index and peeling from the core wire. . For this reason, the optical transmission fiber having a silicone resin as a sheath material is limited in use, and it is unsuitable for use in oil such as a transformer and a thyristor. In addition, since the silicone resin composition before curing has a short pot life and its viscosity increases with time, the coating speed and the temperature of the atmosphere must be controlled in order to coat the core wire with a constant film thickness. There was a work-related drawback. Furthermore, the refractive index of silicone resin is 1.
The limit is about 40, and there is a drawback in that it is insufficient in performance as a sheath material for a large-diameter optical transmission fiber that is required in accordance with the increase in communication capacity.

On the other hand, the fluorine-containing polymer described in (2) and (3) has a low refractive index of about 1.36, and is therefore more suitable than the silicone resin as the sheath material of the large-diameter optical transmission fiber. However, as shown in (2) and (3), in the conventional method of forming a sheath portion with a fluorine-containing polymer, the core wire and the sheath portion are composite-spun at high temperature, or a fibrous shape is obtained. Since the shaped core wire is coated with the melt or solution of the fluorine-containing polymer, the diameter of the core wire and the thickness of the sheath portion are likely to be uneven. For this reason, there is a problem that light is scattered at the locally bent portion of the interface between the core portion and the sheath portion, resulting in a large transmission loss.
Further, in the optical transmission fiber formed by these conventional methods, the adhesion between the core portion and the sheath portion is not always sufficient, and delamination is likely to occur due to various external factors such as bending, pressure change, and temperature change. There was a problem with durability. Furthermore, in the method for producing an optical transmission fiber by applying a melt or solution of a fluorine polymer as shown in (2) and (3), it takes a long time to cure the sheath portion and the solution application method. In particular, since there is a need to completely remove the solvent out of the system, there are drawbacks in productivity, safety, economy, etc., such as a complicated manufacturing process and equipment.

As described above, in terms of performance such as mechanical strength and adhesion, and in the production of optical transmission fibers, a sheath material that is satisfactory in terms of productivity, safety, economical efficiency, etc. Enables caliber. In the present situation, no sheath material having a lower refractive index has been found.

The present inventors, as a result of earnest research to solve the above problems, fluorine-containing polymer having a fluorine atom content of 30 wt% or more, and fluorine-containing reactive monomer It was found that a cured product of the resin composition characterized by the above-mentioned active energy ray is superior in mechanical strength, adhesion to the core wire and the like as compared with the conventional sheath material of the optical transmission fiber.

Furthermore, in a resin composition characterized by containing a fluorine-containing polymer having a fluorine atom content of 30% by weight, and a fluorine-based reactive monomer, the degree of polymerization of the fluorine-containing polymer Since the viscosity of the resin composition can be arbitrarily controlled by adjusting the content of the resin composition and / or the content thereof, a resin composition having a viscosity matching the coating thickness required for the coating equipment and the core wire can be easily prepared. By increasing the fluorine atom content in the elementary polymer, it is possible to obtain a higher numerical aperture and a larger diameter of the optical transmission fiber, and to obtain a sheath material with a refractive index of about 1.33. The advantages were discovered and the present invention was completed.

That is, the present invention is characterized by containing a fluorine-containing polymer (A) having a fluorine atom content of 30% by weight or more and a fluorine-based reactive monomer (B), and having a refractive index of 1.44. An active energy ray-curable resin composition that gives the following cured product is provided. The above fluorine-containing polymer (A) has the following general formula (I) having a fluorine atom content of 30% by weight or more. [In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms,
A partially fluorinated aliphatic group or an intervening oxygen atom in the main chain thereof, wherein R ₁ is H, CH ₃ , Cl, F or −
X-Rf, and X represents a divalent linking group. ] A polymer of fluorine (meth) acrylate (a) represented by, or the fluorine-containing (meth) acrylate (a) and α,
A copolymer of the β-ethylenically unsaturated dicarboxylic acid ester monomer (b) and / or the vinyl group-containing monomer (c) is used, and the fluorine-based reactive monomer (B) is the above-mentioned. Fluorine-containing (meth) acrylate (a) represented by the general formula (I) and / or the following general formula (III) [In the formula, x represents an integer of 1 to 2, y represents an integer of 4 to 12, and R ₇ represents H, CH ₃ , Cl or F. ] The fluorine-containing (meth) acrylate (d) represented by

The active energy ray-curable resin composition according to the present invention contains essential components of a fluorine-containing polymer (A) having a fluorine atom content of 30% by weight or more and a fluorine-based reactive monomer (B). Other than the above, a non-fluorine-based monomer (C), an additive (D), and a photopolymerization initiator (E) may be contained, if necessary.

In the present invention, from the viewpoint of compatibility with the fluorine-based reactive momer (B) and the non-fluorine-based monomer (C),
The fluorine-containing polymer (A) has a fluorine atom content of 30.
Fluorine-containing acrylate or methacrylate of more than wt% (hereinafter, acrylate and methacrylate are combined,
Abbreviated as (meth) acrylate. ) A polymer of (a),
Alternatively, it is selected from among fluorine-containing (meth) acrylates (a) and ester monomers (b) and / or vinyl group-containing monomers (c) of α, β-ethylenically unsaturated dicarboxylic acids such as fumaric acid and maleic acid. A copolymer with one or more kinds of monomers is used. Among these, the introduction of the α, β-ethylenically unsaturated dicarboxylic acid ester monomer (b) into the fluorine-containing polymer (A) reduces the crystallinity and transparency of the fluorine-containing polymer (A). Of the fluorine-containing reactive monomer (B) and the non-fluorine-containing monomer (C), and a cured resin obtained by irradiating the resin composition according to the present invention with active energy rays,
That is, it is extremely effective in improving the transparency and flexibility of the sheath material. The introduction of the vinyl group-containing monomer (c) into the fluorine-containing polymer (A) also reduces the crystallinity of the fluorine-containing polymer (A), improves the transparency, and the fluorine-based reactive monomer (B). And improving the compatibility with the non-fluorine-based monomer (C), and improving the transparency and flexibility of a cured resin obtained by irradiating the resin composition according to the present invention with an active energy ray, that is, a sheath material. It is valid. Α, β in the fluorine-containing aggregate (A)
The copolymerization ratio of the ester monomer (b) of the ethylenically unsaturated dicarboxylic acid and / or the vinyl group-containing monomer (c) is such that the fluorine atom content of the fluorine-containing polymer (A) is less than 30% by weight. If not, there is no particular limitation. When the fluorine atom content of the fluorine-containing polymer (A) is less than 30% by weight, poor compatibility with the fluorine-based reactive monomer (B) occurs and the cured resin obtained after irradiation with active energy rays is transparent. The property is remarkably deteriorated, and it cannot be used as a sheath material for an optical transmission fiber. The molecular weight of the fluorine-containing polymer (A) is not particularly limited, but for the purpose of imparting a viscosity to the resin composition according to the present invention to the extent that it can be applied to the optical transmission fiber core wire, the number average molecular weight n It is preferable that the number is 1,000 or more. The fluorine-containing polymer (A) is essential for imparting to the resin composition according to the present invention a viscosity that can be applied to the optical transmission fiber core wire,
If the fluorine-containing polymer (A) is lacking, coating becomes extremely difficult and the optical transmission fiber becomes poor.

The fluorine-containing (meth) acrylate (a) has a fluorine atom content of 30% by weight or more, and is represented by the general formula [In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated aliphatic group, and an oxygen atom intervenes in the main chain, for example, Etc., R ₁ is H, CH ₃ , Cl, F or —X—Rf, X is a divalent linking group, specifically (CH ₂ ) n, (However, n is an integer of 1 to 10, and R ₂ is H or an alkyl group having 1 to 6 carbon atoms.), Is. ] The compound represented by is used. More specific examples of these include the following.

a-1 CH ₂ = CHCOOCH ₂ CH ₂ C ₈ F ₁₇ a-3 CH ₂ = CHCOOCH ₂ CH ₂ C ₆ F ₁₃ a-16 CH ₂ = CHCOOCH ₂ CF ₃ a-20 CH ₂ CHCOOCH ₂ C ₂₀ F ₄₁ a-24 CH ₂ = CHCOOCH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ a−28 CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ H As the fluorine-containing (meth) acrylate (a), two or more kinds of compounds having different structures may be used. Further, it goes without saying that the present invention is not limited to the above specific examples.

Specific examples of the ester monomer (b) of α, β-ethylenically unsaturated dicarboxylic acid include the general formula R ₅ OOC (R ₃ ) C═C (R ₄ ) COOR ₆ (II) [wherein R ₃ , R ₄ is H, F, Cl, or CH ₃ , R ₃ and R ₄ may be the same or different, R ₅ and R ₆ are H, or an alkyl group having 1 to 20 carbon atoms or fluorine. R ₅ and R ₆ may be the same or different, but when either one is H, it is a group other than H of the other. ] The compound represented by these is mentioned. Among these R ₅ , R
_{When 6} is an alkyl group, its carbon number is compatible with fluorine-containing (meth) acrylate (a), transparency of fluorine-containing polymer (A), non-crystallinity, and fluorine-based reactivity. From the viewpoint of the compatibility with the monomer (B) and the resin obtained by curing after irradiation with active energy, that is, the sheath material, 3 to 8 resins are particularly preferable from the viewpoint of transparency.

The following compounds may be mentioned as more specific examples of the ester monomer (b) of α, β-ethylenically unsaturated dicarboxylic acid.

b-1 Fumaric acid diethyl ester b-2 Fumaric acid di-n-butyl ester b-3 Fumaric acid di-iso-butyl ester b-4 Fumaric acid di-t-butyl ester b-5 Fumaric acid dipropyl ester b- 6 Fumardi-2-ethylhexyl ester b-7 Fumaric acid dihexyl ester b-8 Fumaric acid ethyl butyl ester b-9 Maleic acid dibutyl ester b-10 Maleic acid dioleyl ester b-11 Fumaric acid n-butyl, t-butyl ester b-12 Ethyl fumarate, iso-butyl ester Needless to say, the present invention is not limited to these specific examples.

The vinyl group-containing monomer (c) is roughly classified into those containing one or more vinyl groups in the molecule, and the form of introducing the vinyl group into the molecule is an acryloyl group or a methacryloyl group. Is also good.

Specific examples of the vinyl group-containing monomer (c) containing one vinyl group in the molecule include: c-1 styrene c-2 nucleus-substituted methylstyrene c-3 nucleus-substituted methoxystyrene c-4 N-vinylpyrrolidone c- 5 N-vinylcaprolactam c-6 acrylonitrile c-7 (meth) acrylic acid c-8 methyl (meth) acrylate c-9 ethyl (meth) acrylate c-10 n-propyl (meth) acrylate c-11 iso-propyl ( (Meth) acrylate c-12 n-butyl (meth) acrylate c-13 iso-butyl (meth) acrylate c-14 t-butyl (meth) acrylate c-15 hexyl (meth) acrylate c-16 2-ethylhexyl (meth) Acrylate c-17 Ethylcarbitol (meth) acrylate c-18 Methyltriglycol (meth) Crylate c-19 Methyl propylene glycol (meth) acrylate c-20 Methyl dipropylene glycol (meth) acrylate c-21 Methyl tripropylene glycol (meth) acrylate, c-22 Polypropylene glycol mono (meth) acrylate, (Number average molecular weight 150 To 1000) c-23 stearyl (meth) acrylate c-24 phenoxyethyl (meth) acrylate c-25 ethoxyethyl (meth) acrylate c-26 methoxyethyl (meth) acrylate c-27 butoxyethyl (meth) acrylate c-28 N , N-diethylaminoethyl (meth) acrylate c-29 N, N-dimethylaminoethyl (meth) acrylate c-30 glycidyl (meth) acrylate c-31 allyl (meth) acrylate c-32 2-hydroxyethyl (meth) a Relate c-33 2-hydroxyethyl (meth) acrylate c-34 2-methoxyethoxyethyl (meth) acrylate, c-35 2-ethoxyethoxyethyl (meth) acrylate c-36 benzyl (meth) acrylate c-37 cyclohexyl ( (Meth) acrylate c-38 dicyclopentenyl (meth) acrylate c-39 dicyclopentenyloxyethyl (meth) acrylate c-40 2-hydroxyethyl (meth) acryloyl phosphate c-41 tetrahydrofurfuryl (meth) acrylate c- 42 dicyclopentadienyl (meth) acrylate c-43 dicyclopentadiene ethoxy (meth) acrylate c-44 p-benzylphenoxyethyl (meth) acrylate c-45 1,6-hexanediol mono (meth) acrylate c −46 Neo Nethyl glycol mono (meth) acrylate c-47 Glycerin mono (meth) acrylate c-48 Trimethylolpropane mono (meth) acrylate c-49 Pentaerythritol mono (meth) acrylate c-50 2-Hydroxy-3-phenyloxy Propyl (meth) acrylate c-51 2-hydroxy-3-octyloxypropyl (meth) acrylate c-52 Diethylene glycol mono (meth) acrylate c-53 Polyethylene glycol (400) mono (meth)
Acrylate c-54 Methyl polypropylene glycol mono (meth)
Acrylate (number average molecular weight 150-1000) A specific example of the vinyl group-containing monomer (c) containing two or more vinyl groups in the molecule is a polyvalent (meth) acrylate in which two or more (meth) acrylic acids are bonded to a polyhydric alcohol, and more specifically Specific compounds include the following compounds.

c-58 ethylene glycol di (meth) acrylate c-59 diethylene glycol di (meth) acrylate c-60 triethylene glycol di (meth) acrylate c-61 polyethylene glycol di (meth) acrylate (number average molecular weight 150 to 1000) c- 62 propylene glycol di (meth) acrylate c-63 dipropylene glycol di (meth) acrylate c-64 tripropylene glycol di (meth) acrylate c-65 polypropylene glycol di (meth) acrylate (number average molecular weight 200 to 1000) c- 66 Neopentyl glycol di (meth) acrylate c-67 1,3-butanediol di (meth) acrylate c-68 1,4-butanediol di (meth) acrylate c-69 1,6-hexanediol di (meth) acrylate Acrylate c-70 Hydroxypivalic acid Ester neopentyl glycol di (meth) acrylate c-73 bisphenol A di (meth) acrylate c-74 trimethylolpropane tri (meth) acrylate c-75 pentaerythritol tri (meth) acrylate c-76 dipentaerythritol hexa (meth) acrylate c-77 pentaerythritol tetra ( (Meth) acrylate c-78 trimethylolpropane di (meth) acrylate c-79 dipentaerythritol monohydroxypenta (meth) acrylate In addition to the above, as the vinyl group-containing monomer (c), neomer NA-305, neomer BA-601 , Neomar TA-505,
Neomar TA-401, Neomar PHA405X, Neomar TA705X,
NEOMER EA400X, NEOMER EE401X, NEOMER EP405X, NEOMER HB601X, NEOMER HB605X (above, Sanyo Chemical Industry Co., Ltd.), KAYARAD HX-220, HX-620, D-310, D
-320, D-330, DPHA, DPCA-20, DPCA-30, DPCA-6
0, DPCA-120 (above, manufactured by Nippon Kayaku Co., Ltd.). According to the knowledge of the present inventors, from the viewpoint of the transparency of the resin after curing, among the above specific examples, the vinyl group-containing monomer (c) is particularly preferably one containing a methyl group in the molecule. . Further, as the vinyl group-containing monomer (c), a single compound may be used, or two or more kinds of compounds having different structures may be used.

Needless to say, the present invention is not limited to the above specific examples.

The fluorine-containing polymer (A) according to the present invention is produced by a polymerization method known in the art, for example, a method such as radical polymerization, anionic polymerization or cationic polymerization, using heat, light, electron beam, radiation or the like as polymerization initiation energy. However, industrially, radical polymerization using heat and / or light as polymerization initiation energy is preferable. Any of bulk polymerization, solution polymerization, and emulsion polymerization can be adopted as the polymerization form by these polymerization methods. When using heat as polymerization initiation energy, a catalyst-free or azobisisobutyronitrile, benzoyl peroxide, polymerization initiator such as methyl ethyl ketone peroxide-cobalt naphthenate, or when utilizing light such as ultraviolet rays , A so-called photopolymerization initiator known in the art (for example, compounds shown in E-1 to 11 described below) and a photosensitizer such as an amine compound or a phosphorus compound, if necessary, are added to perform polymerization. Can be made faster. Further, in these radical polymerizations, lauryl mercaptan, octyl thioglycolate, C ₈ F ₁₇ CH ₂ CH ₂ S may be added as necessary.
By using a chain transfer agent such as H together, the degree of polymerization of the fluorine-containing polymer (A) can be adjusted. When polymerizing and curing with an electron beam or radiation, addition of a polymerization initiator or the like is not particularly required.

When the fluorine-containing polymer (A) is obtained by solution polymerization,
The solvent is not limited as long as it does not adversely affect the polymerization reaction.

The fluorine-based reactive monomer (B) according to the present invention can be polymerized in the presence or absence of a photopolymerization initiator, and as a typical specific example, it contains a compound represented by the general formula (I). Fluorine (meth) acrylate may be mentioned. Among these, in consideration of the dilutability of the fluorine-containing polymer (A) and the transparency of the resin after curing, in the compound of the general formula (I), Rf has 1 to 12 carbon atoms, and 2 Valuable linking group is-
CH ₂ −, −CH ₂ CH ₂ −, Etc. are preferred.

Furthermore, the general formula [In the formula, x represents an integer of 1 to 2, y represents an integer of 4 to 12, and R ₇ is H, CH 3, Cl, or F. ] The fluorine-containing (meth) acrylate (d) represented by the following formula can also be used as the fluorine-based reactive monomer (B). Specific examples of these include the following.

_{B-1 CH 2 = C (} CH 3) COOC 2 H 4 (CF 2) 4 C 2 H 4 OCOC (C
_{H 3) = CH 2 B-} 2 CH 2 = C (CH 3) COOC 2 H 4 (CF 2) 6 C 2 H 4 OCOC (C
_{H 3) = CH 2 B-} 3 CH 2 = C (CH 3) COOC 2 H 4 (CF 2) 12 C 2 H 4 OCOC (CH
₃ ) = CH ₂ The fluorine-based reactive monomer (B) does not necessarily have to be a single compound, and may be a mixture of two or more kinds of compounds having different structures.

The proportion of the fluorine-based reactive monomer in the resin composition of the present invention is preferably 10% by weight or more from the viewpoint of the transparency of the resin after curing. If it is less than 10% by weight, transmission loss due to turbidity of the resin occurs.

The non-fluorine-based monomer (C) is used for the purpose of imparting transparency, flexibility, toughness and the like of the resin after curing the active energy ray-curable resin composition according to the present invention, and for curing the resin. It is extremely important for the purpose of adjusting the refractive index, and the proportion occupied in the resin composition according to the present invention is not particularly limited, but 50% by weight or less is preferable for the purpose of controlling the refractive index to 1.44 or less.

The non-fluorine-based monomer (C) may be the same as the vinyl group-containing monomer (C). However, from the viewpoint of imparting transparency, flexibility, and toughness to the resin after curing and the compatibility with the fluorine-based reactive monomer (B), according to the knowledge of the present inventors, the molecule has 1
It is more preferable to have one or more methyl groups and to contain one or more methacryloyl groups or acryloyl groups. Typical representative examples of these are the above-mentioned c-10,11,12,13,14,17,19,20,21,22,26,27,
34,35,46,48,54,55,56,57,62,63,64,65,66,67,70,71,7
2,74,78 etc., Neomer NA-305, TA-505, PHA405X, TA
705X, EP405X, HB605X (above, Sanyo Chemical Industry Co., Ltd.)
Etc.

The non-fluorine-based monomer (C) does not necessarily have to be a single compound, and may be a mixture of two or more kinds of compounds having different structures. Further, it goes without saying that the present invention is not limited to the above specific examples.

Examples of the additive (D) according to the present invention include a solvent for adjusting viscosity, a light resistance stabilizer, a coupling agent and other additives for improving adhesion to the optical transmission fiber core wire,
Examples thereof include an antifoaming agent, a leveling agent, and a surfactant for evenly applying to the core wire. The antifoaming agent, the leveling agent, and the surfactant are preferably fluorine-based ones.

The active energy ray-curable resin composition according to the present invention and an additive (D) for the purpose of improving transparency, plasticizing, etc. while reducing the refractive index of the resin obtained by curing the resin composition. As other than the above, a non-polymerizable fluorine compound,
For example _{HO (CH 2) r C S} F 2s + 1 (r is an integer from 1 to 4, s is an integer from 1 to 20.) Such as hydrofluoric fluorinated _{alcohol, HOOC (CH 2) t C} u F _{2u + 1} (t is 0 or 1 to 4
And u is an integer of 1-20. ) Such as fluorinated carboxylic acids, fluorinated polyethers commonly referred to as fluorinated oils, N (C ₄ H ₉ ) ₃ , perfluorodecalin, C ₈ F ₁₇ OC ₄ F ₉ , C ₉ F ₂₀ Compounds commonly referred to as fluorine-based inert liquids such as The proportion of this non-polymerizable fluorine compound additive in the active energy ray-curable resin composition is preferably 30% by weight or less, and 20% by weight or less because the strength of the resin after curing decreases if excessively added. Is more preferable.

The active energy ray-curable resin composition according to the present invention,
After coating or impregnating the base material, especially the optical transmission fiber core wire, it is polymerized and cured by irradiating with active energy rays such as light, electron beam, and radiation to form a desired coating film, for example, a sheath material. In some cases, heat can also be used as an energy source. When light such as ultraviolet rays is used as the active energy ray, a photopolymerization initiator (E) known in the art, for example, E-1: benzophenone, E
-2: acetophenone: E-3: benzoin, E-4: benzoin ethyl ether, E-5: benzoin isobutyl ether, E-6: benzyl methyl ketal, E-7: azobisisobutyronitrile, E-8: 1-hydroxycyclohexylphenyl ketone, E-9: 2-hydroxy-2-methyl-1-phenylpropan-1-one, E-10: 1- (4 '
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, E-11: 1- (4'-dodecyl-
(Phenyl) -2-hydroxy-2-methylpropane-1
It is preferable to use -one or the like as a catalyst. Also,
If necessary, a photosensitizer such as an amine compound or a phosphorus compound can be added to accelerate the polymerization. The suitable ratio of the photopolymerization initiator in the active energy ray-curable resin composition according to the present invention is 0.01 to 10% by weight, more preferably 0.1 to 7% by weight. When polymerizing and curing with an electron beam or radiation, addition of a polymerization initiator or the like is not particularly required.

As mentioned above, the solvent can be added in order to control the viscosity, coatability, and film thickness of the coating composition of the present invention. Such a solvent is not particularly limited as long as it does not adversely affect the polymerization reactivity of the composition of the present invention, but is not limited to alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, Ester type such as methyl acetate, ethyl acetate, butyl acetate, chlorine type such as chloroform, dichloroethane, carbon tetrachloride, and benzotrifluoride, chlorobenzotrifluoride, m-xylenehexafluoride, tetrachlorodifluoroethane, A low boiling point solvent such as 1,1,2-trichloro-1,2,2-trifluoroethane or trichloromonofluoromethane is preferable from the viewpoint of workability.

When the active energy ray-curable resin composition of the present invention is applied to or impregnated into a substrate as a solution dissolved in a solvent, it is removed at room temperature, or if necessary, by heating or depressurizing before starting polymerization and curing. A step of making it a solvent is required. When the solvent is removed by heating, it is preferable to carry out the heating at 80 ° C. or lower in order to prevent the heat polymerization of the monomers and the like.

As a method for applying the energy ray-curable resin composition according to the present invention to a substrate, various methods known in the art, for example, a brush coating, an applicator, a per coater, a roller brush, a roll coater or the like coating method, air. A spray coating method using a spray or airless spray coating machine, a flow coating method using a shower coater or a curtain flow coater (flow coating), a dipping method, a casting method, and a spinner coating method can be used. It is desirable to use them properly according to the material, shape, application, etc.

In the resin composition of the present invention, by adjusting the ratio of each component as described above, a resin having a refractive index suitable for the purpose can be easily obtained, and a transparent resin having a refractive index of about 1.33 can be obtained. Therefore, the numerical aperture of the optical transmission fiber has increased,
It is possible to increase the diameter.

The resin composition of the present invention is used not only for the sheath material of an optical transmission fiber, but also for its low refractive index, and is applied to the surface of a transparent substrate such as glass or transparent plastic to form a low reflectance coating. You can also do it.

Furthermore, the resin composition of the present invention has scratch resistance, oil resistance,
Since it forms a cured film with excellent smoothness, anti-friction property, water / oil repellency, water resistance, moisture resistance, rust resistance, stain resistance, releasability, release property, and low water absorption, various materials and It can also be used as a protective coating film for a substrate.

For example, copper, aluminum, non-magnetic metals such as zinc and polyethylene terephthalate, polyesters such as polyethylene-2,6-naphthalate, polyolefins such as polypropylene, plastics such as cellulose derivative polycarbonate such as cellulose acetate, and further, Ferromagnetic alloy deposited on ceramics such as glass, paper, wood, fiber, porcelain and pottery (based on iron, cobalt and / or nickel, with a small amount of aluminum, silicon, chromium, manganese, molybdenum, titanium) , Various heavy metals, rare earth metals, etc.) or magnetic tape such as iron, cobalt, chromium, etc. deposited on a plastic film such as polyester in the presence of a trace amount of oxygen, or a protective coating for the magnetic layer of a magnetic disk, etc. Or
It is also suitable as a surface and back surface treatment agent for magnetic recording media such as magnetic tapes and floppy discs, which are required to have antifriction properties.

On the other hand, since the resin composition of the present invention can form a transparent and smooth thin film on the glass surface, it can be used for applications requiring oil resistance and wiping resistance as an oil stain preventive agent for various optical devices. can do.

Further, it is also suitable as a protective coating for a solar cell protective film, an optical fiber, an optical fiber cable, an optical disc, a magneto-optical disc, etc., which is particularly required to have moisture resistance. Further, since it is excellent in scratch resistance, antifouling property, and moisture resistance, it can be used as surface protection for medical devices and instruments, surface protection for teeth and dentures, tooth cavities and molds.

Further, since the resin composition of the present invention can form a film having excellent scratch resistance, it can be used as a hard coating agent for various molded products or films, sheets and the like.

Furthermore, a pigment and a dispersant can be mixed into the resin composition of the present invention to form a paint or ink excellent in antifouling property or non-tackiness.

Next, specific synthesis examples and examples of the present invention will be described, but it goes without saying that the present invention is not limited to these explanations. In the text, "part" and "%" are based on weight.

The performance of the cured resin obtained by irradiation with active energy rays was evaluated by the following method.

Adhesion evaluation Polymethylmethacrylate plate (Mitsubishi Rayon Co., Ltd.
rewrite L- # 001, board thickness 2mm), polystyrene board (da
U-Chemical Styron, plate thickness 2mm) and glass plate (plate)
According to the present invention, the cured film thickness is 100 μm for a thickness of 5 mm).
An active energy ray curable resin was applied.

A two-lamp condensing type high-pressure mercury lamp (160 W / cm) was used as an active energy ray source, and cured at a conveyor speed of 200 m / min.

In the case of the comparative hot-melt type fluorine-containing resin, a film having a thickness of 100 μm was obtained from a heat press at a pressure of 100 kg / cm ² at 200 ° C. for 5 minutes, and the film was laminated on each substrate surface, and at 230 ° C. for 10 seconds. , 5kg
It was pressure-bonded and laminated under the condition of / cm ² .

The adhesion test of the sample obtained in this way was carried out according to JIS5400
It was evaluated according to the evaluation criteria according to.

Evaluation of optical transmission property The optical transmission capability of the optical transmission fiber is described in JP-A-58-7602, No. 4.
The transmission loss (dB / transmission distance) was measured and evaluated with the same type of equipment as shown in the figure. The measurement conditions are as follows.

Interference filter (main wavelength) 650 μm Total length of optical transmission fiber 5 m Cutting length of optical transmission fiber 4 m Bobbin diameter 190 mm Mandrel test To evaluate the adhesion and toughness of the sheath material to the optical transmission fiber core, light is applied to a 5 mm diameter mandrel. The transmission fiber was wrapped around and magnified with a microscope, and the adhesion between the optical transmission fiber core wire and the sheath material and the presence or absence of cracking in the sheath material portion were observed, and the evaluation was made in the following three stages.

Evaluation point 3: No change in adhesion between the core part and the sheath part and generation of cracks in the sheath part were observed.

2: A slight change in adhesion between the core portion and the sheath portion and / or occurrence of cracks in the sheath portion is observed.

1: Peeling between the core part and the sheath part and / or cracking in the sheath part is observed. Hereinafter, all compound abbreviations refer to the above compounds. Also, Ac after the abbreviation is an acrylate compound, Mac
Indicates that it is a methacrylate compound.

Synthesis Example 1 Synthesis of a-1 / b-2 / c-12 (Ac) copolymer 90 5 5 (%) 500 ml 4 equipped with cooling condenser, thermometer and stirrer
In a one-necked round bottom flask, a-1 180g, b-2 10g, c
-12 10 g, and azobisisobutyronitrile (hereinafter A
It is called IBN. ) 1 g is weighed and stored in an N ₂ gas atmosphere at 70 ° C for 30
Stir for minutes. After further stirring at 120 ° C. for 5 minutes, the viscous massive polymer was taken out of the system when heated.

The molecular weight calculated from GPC was n = 920,000 in terms of styrene. The fluorine atom content was 56.1%. The polymer is transparent in an atmosphere of 25 ° C, and the refractive index ▲ n ²⁵ _D ▼ is 1.368.
Met.

Hereinafter, the molecular weight and refractive index of the fluorine-containing polymer synthesized in the same manner as in Synthesis Example 1 are summarized in Table-1.

Synthesis Example 10 Synthesis of a-3 / b-17 / c-14 (Mac) Copolymer 80/10/10 (%) In a 500 ml four-neck round bottom flask equipped with a cooling condenser, a thermometer and a stirrer, a -3 80g, b-17 10g, c-14
(Mac) 10g, and lauryl mercaptan 1g, AIBN0.3
230 g of g, 1,1,1-trichloroethane was weighed and reacted at 80 ° C. for 10 hours in a N ₂ gas atmosphere. The solvent is distilled off under reduced pressure,
The desired polymer was obtained.

n = 11 Man, was ▲ n ²⁵ _D ▼ = 1.371.

Hereinafter, the molecular weight and refractive index of the fluorine-containing polymer synthesized in the same manner as in Synthesis Example 10 are summarized in Table-2.

Synthesis Example 13 Synthesis of a-1 / c-46 (Mac) copolymer 95/5 (%) In a 500 ml glass cylindrical flask equipped with a stirrer, a
-1 380g, c-46 (Mac) 20g, octyl thioglycolate 2g, and E-9 12g as a photopolymerization initiator are weighed and stirred at 60 ° C, and a fluorescent 60W 2 lamp for UV rays is used from the side. It was irradiated and reacted for 1 hour. By this operation at 80 ℃
A 200 ps viscous polymer was obtained. Since it is a crosslinked polymer, the molecular weight could not be measured by GPC. Fluorine content is 59.2%
Met. By gas chromatography, 24% of the total unreacted monomer remained. The refractive index n _D is 1.35
Was 2.

Comparative Synthesis Example 1 In the same manner as in Synthesis Example 1, a-1 / b-2 / c-12 (Ac) 40/3
Copolymerization was carried out at a composition of 0/30 (%). The resulting polymer had a fluorine atom content of 24.9%, a styrene-equivalent molecular weight n = 910,000, and a refractive index ▲ n ²⁵ _D ▼ of 1.451.

Examples 1 to 13 and Comparative Examples 1 to 4 Fluorine-containing polymers obtained in Synthesis Examples 1 to 13 and Comparative Synthesis Example A), fluorine-based reactive monomers (B), non-fluorine-based monomers ( An active energy ray-curable resin composition was prepared using C), the additive (D), and the photopolymerization initiator (E).

Application Examples 1 to 13 and Comparative Application Examples 1 to 7 Adhesion of the above resin composition and other known compositions to polymethylmethacrylate plate, polystyrene plate, and glass plate, and for the sheath material of the optical transmission fiber. Various properties when the above are provided are summarized in Tables 1, 3, 2 and 4 of Table 3.

When the active energy ray-curable resin composition is used, the optical transmission fiber core wire is continuously immersed in the bath of the resin composition and pulled up, at a drawing speed of 300 m / min, 160 W / min.
Ultraviolet rays were radiated from 3 cm high pressure mercury lamp condensing type lamps to form an optical transmission fiber.

The optical transmission fibers shown in Comparative Application Examples 5 and 6 were formed by applying a fluorine-based polymer melted at the temperature shown in the table to the optical transmission fiber core wire and air-cooling.

Moreover, the curing of the silicone resin shown in Comparative Application Example 15 is 15
It was carried out under conditions of 0 ° C. and 1 minute. The drawing speed of the optical transmission fiber in this case is 3 m / min.

In the optical transmission fiber using polymethylmethacrylate and polystyrene as core components, the core wire diameter was 500 μm, and the sheath portion thickness was 40 μm. Further, in the optical transmission fiber using quartz as a core component, the diameter of the core wire was 250 μm, and the thickness of the sheath portion was 30 μm.

In Tables 2 and 4, PM and PS are optical transmission fibers having polymethylmethacrylate and polystyrene as cores, respectively, and G is an optical transmission fiber having quartz as cores.

As is clear from 1, 3, 2 and 4 in Table-3, the active energy ray-curable resin according to the present invention can provide a light transmission fiber which is far superior to the conventional sheath material. Further, from Comparative Examples 1, 2, 3 and 4, it was found that the fluorine-containing polymer according to the present invention is an essential component for obtaining a good quality optical transmission fiber.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C09D 133/16 PDW G02B 6/00 386 391

Claims (1)

[Claims] 1. The following general formula (I) having a fluorine atom content of 30% by weight or more. [In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms,
A partially fluorinated aliphatic group or an intervening oxygen atom in the main chain thereof, wherein R ₁ is H, CH ₃ , Cl, F or −
X-Rf, and X represents a divalent linking group. ] A polymer of fluorine (meth) acrylate (a) represented by, or the fluorine-containing (meth) acrylate (a) and α,
A copolymer of a β-ethylenically unsaturated dicarboxylic acid ester monomer (b) and / or a vinyl group-containing monomer (c), and a fluorine-containing (meth) acrylate (a) represented by the general formula (I). And / or the following general formula (III) [In the formula, x represents an integer of 1 to 2, y represents an integer of 4 to 12, and R ₇ represents H, CH ₃ , Cl or F. ] The fluorine-containing (meth) acrylate (d) represented by these, The active energy ray curable resin composition which gives the hardened | cured material whose refractive index is 1.44 or less.