JPS62199643A - Low-refractive index resin composition and use thereof - Google Patents

Abstract

PURPOSE:A composition showing improved effects as sheathing material of optical fiber and coating, curable with active energy rays to provide a tough, transparent cured material having low refractive index, containing a specific fluoropolymer and a fluorine reactive monomer. CONSTITUTION:A composition comprising a fluoropolymer having >=30wt% fluorine atom content and a fluorine reactive monomer, providing a cured mate rial having <=1.44 refractive index. The composition is applied to fiber core of light transmission, cured with active energy rays to form fiber for light transmission. Poly(tetrafluoroethylene), poly(vinylidene fluoride/tetra fluoroethylene), etc., are used as the fluoropolymer. A fluorine-containing (meth) acrylate, etc., is used as the monomer.

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 rays12, more specifically,
The present invention relates to an active energy ray-curable resin composition that provides a tough and transparent cured resin with a low refractive index upon irradiation with active energy rays.

Fluorine-containing polymers generally have high chemical resistance, weather resistance, water and oil repellency, surface smoothness, etc., and are therefore used as highly functional materials in a variety of fields, but in recent years their use has increased. Its optical properties, that is, its low refractive index, have attracted attention, and its use as a sheath material for optical transmission 7-eyepers and as a low-reflection coating has become active.

Optical transmission fibers are broadly classified into inorganic glass-based fibers and synthetic resin-based fibers, both of which consist of a highly transparent core portion with a high refractive index and a sheath portion with a relatively low refractive index. Hitherto, as a method for forming the sheath portion, coating with a silicone compound or a fluorine-containing polymer having a low refractive index has been proposed and practiced. For example, (1) a method of applying a silicone j 1% resin composition to a drawn quartz core wire and forming a sheath portion of silicone resin by heat curing;
2) Polymerization of a core material such as poly(methyl methacrylate) or poly(styrene) and a hepta-stranded alkyl group-containing (vine) acrylate obtained by a polymerization method such as solution polymerization, bulk polymerization, or emulsion polymerization. Copolymerization, copolymer of (meth)acrylate containing a 7-fluorinated alkyl group and other comonomers, or poly(tetra-70 ethylene), poly(7
A method of forming a sheath portion made of a fluorine-containing polymer by composite spinning with a fluorine-containing polymer such as vinylidene fluoride/tetra-70-ropropylene) or poly(vinylidene-tetra-70-ropropylene) (Koaki U. No. 43-8978, Special Publication No. 1983
-8321, Special Publication No. 56-8322, Special Publication No. 56-
No. 8323, JP-A-59-84203, JP-A-59-
No. 84204, JP-A-59-98116, JP-A-59
-147011, JP-A-59-204002), (
3) Poly(vinylidene heptadide/tetra 70 roethylene) on a quartz-based or plastic-based core wire shaped into a fiber.
There have been proposals for forming a sheath by applying a melt or solution of a fluorine-containing polymer such as (Japanese Patent Publication No. 53-21660, Japanese Patent Publication No. 56-41966).

However, among these proposals, the silicone resin described in (1) has excellent heat resistance but poor oil resistance, and when immersed in mineral oil etc., it has the drawback of causing a change in refractive index and peeling from the core wire.

For this purpose, optical transmission 7 using silicone N (1112 as the sheath material)
Eyepers had limited uses and were unsuitable for use in oil, such as transformers and thyristors.

In addition, the silicone resin composition before curing has a short bottling rate (7), and its viscosity increases over time, so the coating speed and ambient temperature must be controlled in order to coat the core wire with a constant film thickness. There was a drawback in the work that had to be done.

Furthermore, silicone resin has a refractive index of 1.40.
However, there is a drawback that the performance is insufficient for use as a sheath material for large-diameter optical transmission fibers, which are required as communication capacity increases.

On the other hand, the refractive index of the 7-wire-containing polymer described in (2) and (3) is as low as about 1.36, so silicone is used as the sheath material for a large-diameter optical transmission 7-eyeper. However, in the conventional method of forming the w# part with a fluorine-containing polymer as shown in (2) and (3), the core wire and sheath part are separated at high temperature. Because of composite spinning and coating of a fluorine-containing polymer melt or solution on a core wire shaped into a thin shape, the diameter of the core wire and the thickness of the sheath part tend to be uneven. There is a problem in that light scattering occurs at the locally bent portion of the interface between the window portion and the sheath portion, resulting in increased transmission loss. *In addition, in the optical transmission 7 eyepers formed by these conventional methods, the adhesion between the window part and the sheath part is not necessarily sufficient, and delamination may occur due to various external factors such as bending, pressure changes, temperature changes, etc. Because it is easy to use, there are problems with durability, etc.

Furthermore, in the 91R method of optical indicating I transmission fiber by applying a melt or solution of a wire-containing electrical combination as shown in (2) and (3), the WIWS portion is cured.

In addition, the solution coating method has disadvantages in productivity, safety, economy, etc., such as the need to completely remove the solvent from the system, which complicates the manufacturing process and equipment. Ta.

As mentioned above, in terms of performance such as mechanical strength and adhesion, and in the production of optical transmission fiber, productivity
Details Rakuki Ze'Str+ ♂r Ma1 Princess Fortune 1
At present, a sheath material with a lower refractive index that enables higher numerical apertures and larger apertures than 1 or 2 has not yet been found.

As a result of intensive research to solve the above problems, the present inventors have discovered that a fluorine-containing polymer having a fluorine atom content of 30% by weight or more and a heptad reactive monomer. A resin composition cured by active energy rays has superior mechanical strength and adhesion to the core wire compared to the sheath material of conventional optical transmission 7-eyepers, and furthermore, the resin composition is applied to the core wire of the optical transmission 7-eyeper, and cured with active energy rays to create an optical transmission fiber! It has been found that the method of manufacturing is significantly superior to conventional methods in terms of productivity, safety, and economy.

Furthermore, tHII? characterized by containing a fluorine-containing polymer having a fluorine atom content of 301i% or more and a heptadium-based reactive monomer? f In the AIl composition,
Since the viscosity of the resin composition can be controlled without interruption by adjusting the degree of polymerization and/or content of the resin composition, the resin composition has a viscosity that meets the required coating thickness for the coating equipment and core wire. By easily preparing and further increasing the number of heptad atoms in the fluorine-containing polymer, it is possible to increase the numerical aperture of -lC4 and the fiber diameter ratio of the optical transmission fiber. , discovered advantages such as being able to obtain a sheath material with a refractive index of about 1.33, and completed the present invention.

That is, the present invention provides a polymer having a refractive index of 1.44 or less, which is characterized by containing a fluorine-containing polymer having a 7-chain atom content of 30% or more, and a 7-chain reactive monomer. an active energy ray-curable resin composition that provides a cured product; further, the active energy ray-curable resin composition is applied to an optical transmission fiber core wire, and then cured by irradiation with active energy rays to form an optical transmission fiber; There are ways to do this.

The active energy ray-curable resin composition according to the present invention includes:
In addition to the essential components of the t7-strand polymer (A) having a 7-strand atom content of 30% by weight or more and the 7-strand reactive monomer (B), a non-7-strand monomer may be added as necessary. (C), an additive (D), and a light intermediary initiator (L>).

The fluorine-containing polymer (A) is not particularly limited as long as it has a 7-stranded atom content of 30% or more;
0 ethylene), poly(vinyritine heptatonide/hexa70
Lopropylene), poly(par 7aa styrene)! ! Those containing a fluorine atom in the main chain of the polymer such as It is also possible to use a 7-wire epoxy compound such as
However, according to the findings of the present inventors, the hepta-based reactive monomer (B) and the non-hepta-based monomer (C)
From the viewpoint of compatibility with the fluorine-containing polymer (A), fluorine-containing acrylates having a fluorine atom content of 30% by weight or more may also be used as the fluorine-containing polymer (A). < stands for methacrylate (hereinafter, acrylate and methacrylate are collectively abbreviated as (meth)acrylate.

) a polymer of (a) or a 7-chain (meth)acrylate (a) and a, β-, such as 7-chain 1, maleic acid
Ester monomer of ethylenically unsaturated dicarboxylic acid (b
) and/or a vinyl group-containing monomer (e) or a copolymer with a monomer of 2!111 or more is preferred. The introduction of b) into the fluorine-containing polymer (A) reduces the crystallinity of the 7,2'-containing polymer (A), improves transparency, and reduces the fluorine-based reactive monomer (
B) and improved compatibility with the non-heptadol monomer (C),
And the transparency and n
j It is extremely effective for the flexibility direction H. In addition, the introduction of the vinyl group-containing monomer (c) into the fluorine-containing heavy vehicle (A) can also reduce the crystallinity of the fluorine-containing polymer (A), improve the transparency, and reduce the fluorine-containing reactive monomer (B). and improved compatibility with the non-hetazole monomer (C), and the transparency and flexibility of the cured #I resin, that is, the sheath material, obtained by irradiating the resin composition according to the present invention with active energy rays. It is effective in the direction of copolymerization of the ester monomer of a, β-ethylenically unsaturated dicarboxylic acid (b) and the vinyl group-containing monomer ((c)) in the fluorine-containing polymer (A). 'f!: A fluorine-containing polymer (A) without any particular limitation as long as the 7-strand atom content of the fluorine-containing polymer (A) is not less than 30% by weight.
If the 7-chain atom content of A) is less than 30% by weight, poor compatibility with the 7-chain reactive monomer (B) will occur, and the transparency of the cured resin obtained after irradiation with active energy #1 will deteriorate. The material deteriorates so much that it cannot be used as a sheath material for an optical transmission 7-eyeper. The molecular weight of the fluorine-containing polymer (A) is not particularly limited; It is preferable that the amount of Mn is i, o o o or more. The fluorine-containing polymer (A) is essential for imparting viscosity to the resin composition of the present invention to the extent that it can be applied to the optical transmission fiber core, and If the stranded polymer (A) is missing, the coating will be very rough and the optical transmission fiber will be poor quality.

The fluorine-containing (meth)acrylate (a) only needs to have a seven-strand atom content of 30% or more and contain an acryloyl group or a methacryloyl group in the molecule; typical specific examples include , general formula % formula % (1) In the formula 1, l (f is a per-70-roalkyl group or a partially 7-stranded aliphatic group having 1 to 20 carbon atoms, *t=Fl!-stranded atom in the main chain intervention, e.g. -CF2CFO
CF (CF', ), etc. may also be used, and R9 is ■ CF.

H, CI-1, Cl* or F, and X is a divalent linking group, specifically -(CH3)-n.

R7-CHzCI-1-(C)-1zhn*
-(CHz)-nNSO,-.

$ 0■ ■ -((j12″)-nNco (however, n is 1 to 10
R7 is 11 or an alkyl group CII having 1 to 6 carbon atoms.

CH, CH, CI! , CI.

Examples include compounds represented by CF -, CHj and compounds having a plurality of per-70 alkyl groups in the molecule, such as CH2CH*CtF2i+1. More detailed examples of these include the following.

a-I C11*=ClIC0OC112CIItC
sF+tC11°a-2Cl1z=CCOOCHZCII2CsF+ya
-3elf>=C11COOCIlt(:1IzcsP
+sa-4Cl1z=CCOOCIIzCHzCaF+
3C11゜i-5c112=ccoocLcl12c2゜F41a
-6CI+2=CCOOCH*C)I2CJ*C11゜a-7C11,=CC0O-(C1l,hC+oFz+
a-8C11,=ClIC00CIi2CtlCIIz
C*F+tC11°a-9ell, =ccooc112cll-<cll,
hcl@Iko.

C.11.

a-10Cll2=CIICOOCIlzCII2NS
OzCsF+yCIl, cll.

a-11C11t=CCOOCIIzC1lJSOzC
+F+.

I I 11 a-12CIIz=CCOO+Cl2hNS02c+z
FzsC, 11.

a-13C11z=CIICOOCIItCIIJCO
C7F+sllt 薯a (4C11a=CHCOO+CIIzhNCOC+2
FzsC11゜a-15Cl1z=CCOOCIItCF*a(6C1
1t=CIICOOCIIzCF*C11゜a(7CI!2=CCOOCHz(CFthllCll
.

a(8Cll1=CCOOCHiC,F+yC11゜a(9C11i=CCOOCIlzC2oFn+a-2
0C11t=C11COOCII2CzoF<+C11
゜a-21C112=CCOOC1lzCF(CFz)z
a-22Cl1z=CCOOeHzCFIICF*C4
3C112=CCOOCI12C2F5a-24CI+
2=CIICOOCI+24CF2hCF(CF*ha
-2! J C112=CCOOC1lCI'2CFI
ICF31ll C11゜a-26C112=CCOOCIIC10F2゜Js H3 a-27Cl1z=CHCOOC-(C
F 2 hllCll.

a 49 C1l , = CCθOCI+2(:Il
2-(CF21 hl+Vs a-31C112=CIICOOCIICIIF+?C
F3 C11°a-33al12=ccoocLcl12clF13a
-32CHz=C-COOCllzCIIzC*F+y
(2) Cl1zCIIzC*F+ v Two or more types of compounds having different structures may be used as the fluorine-containing (meth)acrylate (a). Furthermore, it goes without saying that the present invention is not limited to the above specific examples.

Specific examples of the ester monomer (b) of a, β-ethylenically unsaturated dicarboxylic acid include the general formula % formula % () 1 where R,, R4 is I-1, F, CI, or C) I
, R1 and R may be the same or different, and R,, R, is H, or a group containing an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, and %
1% and [(, may be the same or different, but when either one is H, f@ is a group other than H. Examples are compounds represented by j. Among these, Rq
, when Rs is an alkyl group, the number of carbon atoms is determined by the following factors: compatibility with the fluorine-containing (meth)acrylate (a), transparency of the fluorine-containing polymer (A), amorphousness, and seven carbon atoms. From the viewpoint of compatibility with the system-reactive monomer (B) and transparency of the resin obtained by curing after irradiation with activated polyurethane, that is, the sheath material, 3 to 8 are particularly preferred.

More detailed examples of the ester monomer (b) of α,β-ethylenically unsaturated dicarboxylic acid include the following compounds.

b-17 Malic acid diethyl ester b-27 Malic acid di-n-butyl ester b-37 Malic acid di-1so-butyl ester b-47 Malic acid co-t-butyl ester b-57 Malic acid dipropyl ester +3-6 7 Marzy 2-ethylhexyl ester b-
77 Malic acid cyhexyl ester b-87 Malic acid ethyl butyl ester b-9 Maleic acid diptyl ester b-10 Maleic acid dioleyl ester b-117 MalWin-butyl, t-butyl ester &-127 Ethyl malate, 1so- Butyl ester C411, OOC11 (so is an integer from 1 to 18) c, Il, 00c HC, 1II00C11 (m is as above) 13-16 CC112CH
2011 (as above) (s as above) H pZp+1 (p% pupil is as above) (p and mouse are as above) Note that the present invention is not limited to these specific examples in any way. Of course.

The vinyl group-containing monomer (C) is roughly divided into those containing one or two or more vinyl groups in the molecule, and the form of vinyl group introduction into the molecule is an acryloyl group or a methacryloyl group. Also good.

Specific examples of vinyl group-containing monomers (c) containing one vinyl group in the molecule include: c-1 styrene c-2-nuclear substituted methylstyrene c-3-nuclear substituted methoxystyrene c-4N-vinylpyrrolidone c-5N - Vinylcaprolactam c-67 Chrylonitrile c-7 (meth)acrylic acid c-8 Methyl (meth)acrylate c-9 Ethyl (meth)acrylate c-10 n-Propyl (meth)acrylate c-111
so-propyl (meth)7 acrylate c-12 n-butyl (meth)acrylate c-131 so-butyl (meth)acrylate c-14 t-butyl (meth)acrylate c-15 hexyl (meth)acrylate c-162-
Ethylhexyl (meth)acrylate c-17 Ethylcarpitol C-18 7-methyl triglycol (meth)acrylate C-19 Methylpropylene glyco-l
Acrylate c-20 Methyl dipropylene glycol (meth) 7
Acrylate c-21 7-tyl tripropylene glycol (meth)
Acrylate, e-22 polypropylene glycol mono(meth)
Acrylate, (number average molecular fi150-1000) c
-23 Stearyl (meth)acrylate c-24
Phenoxyethyl (meth)acrylate c-25
Ethoxyethyl (meth)acrylate c-26 Nodoxyethyl (meth)acrylate tro-27 Butoxyethyl (meth)acrylate c-28 8. N-dimethylaminoethyl (meth)acrylate C49 NJ-dimethylaminoethyl (meth)acrylate c-30 Glycidyl (meth)acrylate C-31
Allyl (meth)acrylate c-32 2-hydroxyethyl (meth)acrylate c-33 2-hydroxyethyl (meth)acrylate c-34 2-
Nodoxyethoxyethyl (meth)acrylate, c-35,2-Dithoxyethoxyethyl (meth)acrylate c-36 Benzyl (meth)acrylate C-37 Cyclohexyl (meth)acrylate c-38 Synclopentenyl (meth)acrylate c- 39 Nocyclopentenyloxyethyl (meth)7 acrylate c-40 2-Hydroxyethyl (meth)acryloyl phosphate c-41 Tetrahydrofurfuryl (meth)acrylate e-42 Dicyclopentadienyl (meth)acrylate c-43 Dicyclopenta Jenethoxy(meth)acrylate c-44g-pen7le7e/xyethyl(meth)acrylate c-451,8-hexanediolmo/(meth)acrylate c-46 neopentyl glycol mono(meth)acrylate c-47 glycerin Mono(meth)7 acrylate c-48
) Limethylolpropanmo/(meth)7 acrylate c-49 Pentaerythritol mono(meth)acrylate c-50 2-Hydroxy-3-phenyloxypropyl (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)
7 acrylate (number average molecular weight 150-1000) C11
30C113 cm56 0 Ctlz
CIl.

C11,OCL el+, 0-CI.

A specific example of the vinyl group-containing monomer (e) containing two or more vinyl groups in the molecule is a polyhydric (meth)acrylate in which two or more (meth)acrylic acids are bonded to a polyhydric alcohol. Examples of typical compounds include the following compounds.

c-58 Ethylene glycol di(meth)acrylate c-59 Diethylene glycol (meth)acrylate c-60) Polyethylene glycol di(meth)acrylate c-61 Polyethylene glycol di(meth)acrylate (number average molecular weight 150-1000) c -827' Robylene glycol di(meth)acrylate c-63 Nopropylene glycol di(meth)acrylate e-64) Lipropylene glycol (methane 7 acrylate c-65 Polyethylene glycol di(meth)acrylate (number average molecular weight 200~ 1000) c-66 neobentyl glycol di(meth)acrylate c-67 1,3-butanediol di(meth)acrylate c-68 1-4-butane quolno(meth)acrylate c-69 1,6-hexane diol di( meth)acrylate c-70 hydroxypivalic acid ester neobentyl glycol di(meth)acrylate C113CII* (R' is H or CH1) e42 R' CHi 0-CHz
CIItCIIsll (R' is ■1 or CHt) C-73 bisphenol di(meth)acrylate c-
74) Limethylolpropane tri(meth)acrylate c-75 Pentaerythritol tri(meth)acrylate c-76 Nopentaerythritol hexa(meth)acrylate c-77 Pentaerythritol tetra(meth)acrylate c-78)'J Methylolpropane (meth)acrylate c-79 dipentaerythritol monohydroxypenta(/acrylate)], vinyl group-containing monomers (c) include Neomer NA-305, Neomer BA-601, Neomer TΔ-505, Neomer TA-401, Neomer PHA
405X, Neomer 'I' A 705X.

Ne: tv-EA400X, $2v-E:E:401X.

Nettv-EP405X, $tv-ILr3601X,
$tv-HB605X (all above, Sanyo Chemical Industries, Ltd. 9I)
), KAYARAD HX-220, HX-620
, D-310, D-320, D-330, L) l'
H.A.

DPCA-20, DPCA-30, DPCA-PiOl
According to the knowledge of the present inventors, from the viewpoint of the transparency of the resin after curing, among the above specific examples, vinyl group-containing monomers As (c), those containing a methyl group in the molecule are particularly preferable.In addition to using a single compound as the vinyl group-containing monomer (c), 2!1 with different structures can be used.
You may use the compound of 4M or more 1-.

It goes without saying that the present invention is not limited to the above specific examples.

The fluoropolymer (A) according to the present invention is produced by a polymerization method known in the art, such as radical polymerization, anionic polymerization, cationic polymerization, etc., using heat, light, electron beam, radiation, etc. as polymerization initiation energy. However, industrially, the heat rises/
Alternatively, radical polymerization in which light is used as the starting energy for heavy intervention is preferable. As the polymerization form by these polymerization methods, either bulk polymerization, W# liquid-based polymerization, or emulsion polymerization can be adopted. 7B When using heat as the starting energy,
Non-catalytic or polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide-cobalt naphthenate, and when using light such as ultraviolet rays, so-called photopolymerization initiators known in the art. (For example, compounds shown in E-1 to E-11 below.)
If necessary, a photosensitizer such as an amine compound or a phosphorus compound can be added to speed up the polymerization. In addition, in these radical polymerizations, 1! such as lauryl mercaptan C=F17CII□CIl, S11, etc. is optionally added. ．． The degree of polymerization of the fluorine-containing polymer (A) can be adjusted by using a chain transfer agent in combination.
vr + wot island ro ke 1- a meeting i 5 stone drama i p ki
When the polymerization is added at a certain time, it is not necessary to add a polymerization initiator or the like.

When obtaining the fluoropolymer (A) by W# liquid polymerization,
There is no limit to the solvent as long as it does not adversely affect the polymerization reaction.

The heptadium-based reactive monomer (B) according to the present invention can be polymerized in the presence or absence of a photopolymerization initiator, and is represented by the general formula (1) as a typical example. Examples include fluorine-containing (meth)acrylates. Among these, considering the dilutability of the fluorine-containing polymer (A) and the transparency of the cured resin, in the compound of the general formula (1), Rf has 1 to 12 carbon atoms and 2 The valent linking group is one CH2-OH Cll.

Cll3　　　　　Cl・°1 etc. are preferred.

Furthermore, in General Formula 1, x represents an integer of 1 to 2, y represents an integer of 4 to 12, and R2 is H, OH3, CI, or F. The compound represented by 1 can also be used as the fluorine-based reactive monomer (B). Specific examples of these include the following.

Low I C11,=C(ell,)C00C211
, (CF2)4C,Il,0COC(CI+,)=C1
1□ C4C11*=C(C11,)C00C211<(CF
2) sczl140cOc(C1l*)=C11°It-3Cll2=C(C11s)C00C211-(
CFt)1□C,ILOCOC(CI+,)=l:ll
7 0-4 C11□”C(CFs)C00Ct11n(
CFCh)<Ca1140COC(CII*)CF3 ;C(1□ B-5GHz = C(CII3nC00C2II, (
L)L)2)4C21140COC(CI+1Il cF.

=CII.

C.F.

0COC(CH3)=CHt (i, b are 1 to 4) The fluorine-based reactive monomer (B) does not necessarily have to be a compound (or a mixture of two or more compounds with different structures). Also good.

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

The non-72I monomer (C) is used for the purpose of imparting transparency, flexibility, toughness, etc. to the resin after curing of the active energy ray-curable resin composition according to the present invention, and for ``curing''. It is extremely important from the viewpoint of adjusting the refractive index of the resin later, and there is no particular restriction on its proportion in the resin composition according to the present invention, but for the purpose of controlling the refractive index to 1.44 or less, it is extremely important. It is preferably less than 1%.

Examples of the non-fluorine monomer (C) include those exactly the same as the vinyl group-containing monomer (C). However, from the viewpoint of imparting transparency, NJ flexibility, and toughness to the cured TT resin, and the use of a fluorine-based reactive monomer (one)
According to the findings of the present inventors, from the viewpoint of compatibility with is more preferable. Typical preferred examples of these include the above-mentioned c 10vl 1 +12,13t1
4*17-19'e20.21,22,26,27,3
4, 35, 46, 4B.

54.55, 56.57.62, 63, 64, 65, 6
6°67.70.71. '72, 74.78, etc., Neomer NA-: (05, 'I''A-505, P I (
A405X.

'r' A 705 X, l・,')' 405
X, H13605X (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

Note that the non-heptad monomer (C) does not necessarily have to be a compound, and may be a mixture of two or more compounds having different structures. Of course, there are no restrictions whatsoever.

Additives (D) according to the present invention include a melt barrel for viscosity gn, a light-resistance stabilizer, a coupling agent and other additives for improving the adhesion with the optical transmission 7 eyeper core wire, and uniformity on the core wire. Antifoaming agents, leveling agents, surfactants, etc. are used for coating. antifoaming agent, leveling agent,
and! As the metastatic agent, fluorine-based agents are preferred.

In addition, for the purpose of improving transparency, nj vfJ (t'; , In addition to the above additives (D), non-polymerizable heptad compounds such as) 10-(CTI, )-CF
(r is an integer from 1 to 4, S is 1 to s 2
g+1 is an integer of 20. ), alcohols such as HO
OCdCHz)-CF (t is 0 * or 1t
u Zu+1 ~1 of 4! Ji loses, and U is an integer from 1 to 20.

), 7-chain carboxylic acids such as 7-chain polyether commonly called 7-chain oil, and N(C411Q)ff
, Bar 70 Lodecalin, CaF170cmF*, C91
・、.

Like! Compounds commonly referred to as heptadine inert liquids can be used. The proportion of this non-polymerizable fluorine compound additive in the active energy ray-curable resin composition is preferably 30% by weight or less, since adding too much will reduce the strength of the cured resin. The following are more preferable.

After the active energy ray-curable resin composition according to the present invention is applied to or impregnated onto a base material, particularly an optical transmission fiber core wire,
By irradiating active energy rays such as light, electron beams, and radiation, it can be polymerized and cured to form a desired coating film, such as a sheath material b.

In some cases, heat can also be used as an energy source. When using light such as ultraviolet rays as active energy rays, photopolymerization initiators (E) known in the art, such as E-1: benzophenone, 1.
E-; (: benzoin, E-4: benzoin ethyl ether, IE-5: benzoin isobutyl ether,
E-6: Bennolmethyl ketal, +>-7: 7zobisisobutyanitrile, E-8: 1-1: l/roxycyclohexylphenyl ketone, E-9: 2-hydroxy-2-methyl-1-phenyl Propan-1-one, E-
1n:1-(4'-isopropylphenyl)-2-hydro-2-methylpropan-1-one, E-11:1
-(4'-dodecyl-phenyl)-2-hydroxy-
It is preferable to use 2-methylpropan-1-one or the like as a catalyst, and if necessary, a photosensitizer such as an amine compound or a phosphorus compound can be added to speed up the polymerization7. The active energy ray curable resin IJLr according to the present invention has a suitable proportion of light weight starting punishment that occupies 1 month of 0.01 to 10%, more preferably 0.1 to 10%.
It is 7 jusun%. When polymerization and curing are carried out using electron beams or radiation, it is not necessary to add a heavy initiator or the like.

The solvent can be used as a target of the present invention as described above. ! Viscosity of 1M composition,
It can be blended to control coating properties and film thickness. There are no particular restrictions on such solvents as long as they do not adversely affect the polymerization reactivity of the composition of the present invention, but esters such as methanol, ethanol, isopropyl alcohol thyl ethyl ketone ketone, methyl acetate, ethyl acetate, butyl acetate, etc. chloroform, dichloroethane, carbon tetrachloride and other chlorine-based compounds, and benzotriflide, chlorobencitri70ide, -1-xylene hexa70lide, tetrachlorocyfuroethane, 1, i, 2-trichloro-1.2 .2-F+7 Low boiling point, alpha solvent such as ethane, trichloromonomethane, etc. is workable, r7.
I like it from I7.

The active energy ray-curable tree IIff of the present invention
, dissolved in a solvent: When applied or impregnated onto a substrate as a liquid, a step of removing the solvent at room temperature or by heating or reducing pressure as necessary is required before starting polymerization and curing. When removing the solvent by heating, it is preferable to remove the solvent at a temperature of 80° C. or lower in order to avoid spoiling the heating polymerization of monomers, etc.

As for the method of applying the hollow lily to the base material, there are methods known in the art, such as brush application, applicator, etc. Coating method using a bar coater, roller brush, or roll coater, spray coating method using an air spray or airless spray coating machine, flow coating method (70-coat) using a shower coater or curtain 70-coater, etc., dipping method , casting method, spinner coating method, etc. can be used, and it is desirable to use them appropriately depending on the material, shape, use, etc. of the base material 7 In particular, optical transmission 7 The resin composition of the present invention is applied to the eyeper core wire and cured. In the case where the optical transmission 7 eyeper core is continuously immersed in a storage tank containing the resin composition according to the present invention and pulled out, the solvent is removed as necessary, and the sheath portion is irradiated with active energy rays. Alternatively, the resin composition of the present invention may be continuously applied through a core of an optical transmission fiber to a cap, the solvent may be removed as necessary, and the resin composition may be irradiated with active energy rays to form a sheath. Method of hardening and forming a part, etc., Dl”2,459,320, JP-A-1983-13;)-13
Methods known in the art, such as those shown in US Pat. No. 9,545, can be used.

When the 84 fat composition of the present invention is polymerized and cured by energy ray irradiation, germicidal lamps, ultraviolet fluorescent lamps, etc. known in the art,
Carbon arc, xenon lamp, high pressure mercury lamp for copying,
Medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, ultraviolet rays from natural light, or electron beams using scanning or curtain-type electron beam acceleration paths can be used, and the thickness is 5 μm. - In the case of UV curing of the coating layer described below, it is preferable to perform the irradiation in an inert gas atmosphere such as nitrogen gas from the viewpoint of increasing the efficiency of polymerization.

Examples of the optical transmission fiber core wire used in the present invention include quartz fibers, and glass fibers such as polymethyl methacrylate, deuterated polymethyl methacrylate, polyethyl methacrylate, polystyrene, and polycarbonate.

The resin composition according to the present invention does not necessarily require thermal energy and is rapidly cured by irradiation with active energy rays, so it is suitable for coating materials that are easily deformed by heat. Particularly when forming the sheath component of an optical transmission fiber, when using a conventional heat-cured zeta-resilicone resin or a hot melt of a black-containing polymer, the sheath component shrinks after curing. There is a drawback that microbending occurs in the optical transmission 7-eyeper, resulting in significant transmission loss. However, according to the method of forming the sheath component using the resin composition of the present invention, the above-mentioned problems are not caused, and there are advantages in terms of quality and yield of the optical transmission 7-eyeper. *According to the optical transmission 7-eyeper forming method according to the present invention, the final drawing speed of the optical transmission fiber is 3 to 6 transport/second, and the manufacturing speed of the optical transmission 7-eyeper is 3 to 5 times that of the conventional method. There are advantages in terms of production. Furthermore, according to the findings of the present inventors, the optical transmission 7-eyeper obtained by the resin composition of the present invention has significantly superior SJF adhesion between the door part and the sheath part compared to conventional ones. Because of this, it has the advantage of being able to withstand usage conditions that involve severe vibration and bending.

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. This has made it possible to increase the numerical aperture and diameter of optical transmission fibers.

The resin composition of the present invention can be applied not only to the sheath material of optical transmission fibers, but also to the surface of transparent substrates such as glass or transparent plastic, taking advantage of its low refractive index, to form a low-reflectance film. You can also.

Furthermore, the tree JJW, IL IAt of the present invention is 1
Scratch resistance, oil resistance, smoothness, antifriction, water and oil repellency, water resistance, moisture resistance, rust prevention, stain resistance, peelability, mold releasability,
Since it forms a cured film with excellent low water absorption, it can also be used as a protective coating film for various materials and substrates.

For example, non-magnetic metals such as copper, aluminum, and zinc, polyesters such as polyethylene terephthalate and polyethylene-2,6-7-talate, polyolefins such as polypropylene, and plastic snacks such as cellulose derivative polycarbonate such as cellulose acetate, In addition, ferromagnetic alloys (based on iron, cobalt and V/or nickel, with small amounts of aluminum, silicon, chromium, Magnetic materials such as iron, cobalt, chromium, etc. are deposited on plastic films such as polyester in the presence of manganese, molybdenum, titanium, rare earth metals, etc. It is also suitable as a protective coating for magnetic layers of magnetic tapes or magnetic disks, and as surface and back surface treatment layers of magnetic recording media such as magnetic tapes and 7A disks, which are required for antifriction properties.

On the other hand, the resin composition of the present invention can form a transparent, smooth, thin film even on the glass surface, so it can be used as an anti-slip agent for various optical vessels, etc., to improve oil resistance and to improve the adhesive properties. It can also be used in applications that require ease of removal.

Furthermore, protective films for solar cells that particularly require moisture resistance, etc.
It is also suitable as a protective coating for fibers, optical fiber cables, optical disks, optical M&A disks, etc. In addition, it has excellent scratch resistance, stain resistance, and 5.1 ltf resistance, so it can be used for medical purposes, as a surface protection for instruments, for protecting the surface of teeth, and for filling and molding of cavities.

Furthermore, since the resin composition of the present invention can form a film with excellent scratch resistance, it can also be used as a hard coating agent for various molded products, films, sheets, etc.

Furthermore, by mixing a pigment and a dispersant into the resin composition of the present invention, a paint or ink with excellent stain resistance or non-stick properties can be formed.

Next, specific synthesis examples and examples of the present invention will be explained, but it goes without saying that the present invention is not limited by such explanations. The performance of the cured I (fat) obtained by irradiation with 6 active energy rays was evaluated by the following method.

Torucho 3fiiPl' (Fly polymethyl methacrylate board (Mitsubishi Ray 92 2m-)
And the cured film thickness is 100μ- on the glass plate (& thickness 5m++)
The active energy ray-curable resin according to the present invention was coated so as to be as follows.

As an active energy ray source, two-lamp concentrating high-pressure water 111
Using light (160W/am), conveyor speed 200
Cured at 1/min.

In the case of a comparative heat-melting type fluorine-containing resin, the thickness was 10% by heating at 200°C for 5 minutes at a pressure of 100kg/c so2.
Obtain a film of 0 μ- and layer it on each base material surface, and
It was laminated by pressure bonding at 5 kg/c-2 for 10 seconds at °C.

The adhesion test of the sample obtained in this way was conducted according to JIS54.
Rated 1. according to the evaluation criteria by 00. Ta.

A work that shines! 111 Optical transmission The optical transmission capability of the 7-eyeper is based on the transmission loss (d
B/km) was measured and evaluated. The measurement conditions are as follows.

A filter (dominant wavelength): 650μ Total length of optical transmission fiber: Cutting length of 5II optical transmission 7 eyeper: 4" - Bobbin diameter: 1
90mmヽz'' 6. Optical Transmission 7 Eyer In order to evaluate the adhesion and toughness of the sheath material to the core wire, 11. An optical transmission 7 Eyer was attached to a mandrel with a diameter of 5 II, and was examined using a microscope. Under magnification, the 1M adhesion of the optical transmission 7 eyeper core #a sheath material and the presence or absence of cracks in the sheath material portion were observed and evaluated on the following three scales.

Evaluation point 3: No change in adhesion between the door portion and sheath portion (4p) and no occurrence of cracks or the like in the sheath portion are observed.

2: Change in ffi adhesion and/or tll between the door part and the sheath part? There is a slight occurrence of cracks etc. in the ¥Is portion.

1: Peeling in the core and sheath parts and/or cracking in the sheath part was observed. From this point on, all compound abbreviations refer to the above-mentioned compounds. In addition, Ac after the abbreviation is an acrylate compound, Ma
c indicates a methacrylate compound.

Synthesis Example 1 Synthesis of a 1/b 2/e 12 (Ac) copolymer 9055 (%) 500 m1 equipped with a cooling condenser, thermometer and stirrer
In a 4 day round bottom flask, a 1 180g 1b 2
10 g, c 12 10 g1 and 1 g of azobisisobutyronitrile (hereinafter referred to as AIBN) were weighed out and stirred at 70° C. for 30 minutes under an N2 gas atmosphere. After further stirring at 120° C. for 5 minutes, the bulk polymer, which was viscous when heated, was taken out of the system.

The molecular weight determined by GPC was Mn=920,000 in terms of styrene. The heptad atom content was 56.1%. 2
The polymer was transparent in an atmosphere at 5°C, and had a refractive index n25 of 1.368.

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 below.

Synthesis Example 10 Synthesis of a3/b17/c i4 (Mac) copolymer 80/10/10 (%) 500m7 equipped with cooling condenser, thermometer and stirrer
4 day round bottom 7 Lasco, a-380g, b-1710g
%a -14 (Mac) 10g,
Weighed out 1 g of Le, 3 g of AIB No., and 230 g of 1゜1.1-trichloroethane, and under an N2 gas atmosphere,
The reaction was carried out at 80°C for 10 hours. The solvent was distilled off under reduced pressure to obtain the desired polymer, Mn = 110,000, no' =
It was 1-371.

The molecular weight and refractive index of the hepta-containing polymer synthesized in the same manner as in Synthesis Example 10 are summarized in Table 2 below.

Synthesis Example 13 Synthesis of a-1/c 46 (Mac) copolymer 9515
(%) A-1380 g, C-46 (Mac) 20 g in a 50011N glass cylindrical flask equipped with a stirrer.

2 g of octyl thioglycolic acid and E-912 as a photopolymerization initiator were weighed out, and while stirring at 60°C, two 60W ultraviolet fluorescent lamps were irradiated from the side to react for 1 hour. This operation yielded a viscous polymer of 200 ps at 80°C. Since it was a cross-tI4 polymer, the molecular flLfJ/i could not be determined by GPC. Fluorine content is 5
6 Chromatography showed that 24% of the unreacted monomer remained in the total weight. *The refractive index nD was 1°352.

Comparative Synthesis Example 1 In the same manner as in Synthesis Example 1, a-'1/b-2/c-
Copolymerization was carried out with a composition of 12(Ac) 40/30/30 (%). The 7-chain atom content of the produced polymer is 24.9
%, the styrene equivalent molecular weight Mn was 910,000, and the refractive index n25 was 1.451.

Examples 1 to 15 and Comparative Examples 1 to 7 Synthesis Examples 1 to 13 and Comparative Synthesis Example 1 Obtained in Synthesis Examples 1 to 13 and Comparative Synthesis Example 1 An active energy ray-curable resin composition was prepared using a monomer (C), an additive (D), and a photopolymerization initiator (E). Table 3 summarizes the adhesion of this resin composition to polymethyl methacryte plates, polystyrene plates, and lath plates, and the im characteristics when used as a sheath material for optical transmission 7 eye bars.

When an active energy ray-curable resin composition is used, the optical transmission fiber core wire is continuously immersed in a bath containing one of the resin compositions, pulled up, and drawn at 300 r for 7 minutes! At one speed, ultraviolet rays were irradiated with three 160 W/c +++ high pressure mercury lamp flame type lamps to form seven light transmission eyebars.

The optical transmission fibers shown in Comparative Examples 5 and 6 were formed by applying a fluoropolymer melted at the temperatures shown in the table to the optical transmission fiber core wire and cooling it in air.

'* Comparative Example 71 The curing of the silicone resin shown was 15
The test was carried out at 0°C for 1 minute. In this case, the drawing speed of the optical transmission 7-eyeper is 3 wheels/min.

In the optical transmission fiber whose core components are polymethylmethacryte and polystyrene, the IK diameter of the core wire was 500 μm, and the thickness of the sheath portion was 40 μm. In addition, in the optical transmission 7-eyeper whose core component is quartz, the diameter of the core wire is 250μ and the thickness of the sheath is 30μ.

In Tables 3 and 4, PM and PS respectively indicate an optical transmission fiber whose core wire is polymethyl methacryte or polystyrene, and G indicates an optical transmission fiber whose core wire is quartz.

As is clear from Tables 3 and 4, the active energy ray-curable resin according to the present invention can provide optical transmission fibers that are significantly superior to conventional sheath materials. Moreover, 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 high-quality optical transmission fiber.

Procedural amendment February 5, 1986

Claims (1)

[Scope of Claims] 1. A fluorine-containing polymer having a fluorine atom content of 30% by weight or more and a fluorine-based reactive monomer, and having a refractive index of 1.44 or less. An active energy ray-curable resin composition that provides a cured product. 2. A resin composition containing a fluorine-containing polymer having a fluorine atom content of 30% by weight or more and a fluorine-based reactive monomer and giving a cured product with a refractive index of 1.44 or less,
A method of coating an optical transmission fiber core wire and then curing it by irradiating it with active energy rays to form an optical transmission fiber.