JPH04356443A - Fluorine-containing (meth)acrylate ester, its production and cured cured product therefrom - Google Patents

Abstract

PURPOSE:To provide a novel fluorine-containing (meth)acrylate ester giving cured products having refractive indexes lower than conventional (meth)acrylate esters and especially useful as a constituting component for UV ray-curable resin compositions used for the clads of optical fibers. CONSTITUTION:A fluorine-containing (meth)acrylate ester of formula I and/or formula II [R1 is CnF2n+1(CH2)a, CnF2n+1(CH2)aO, H(CF2CF2)b(CH2)cO; R2 is H, CH3; (n) is an integer of 1-10; (a) is 0, 1, 2; (b) is an integer of 1-5; (c) is 0, 1), e.g. a compound of formula III or IV. The compound is obtained by reacting a fluorine-containing monoepoxy compound of formula V with (meth) acrylic acid. The compound can readily be polymerized in the presence of heat, UV rays, radiations or a radical polymerization initiator, and can easily be cured by a radical curing system.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to heat, ultraviolet rays, radiation,
The present invention relates to a novel (meth)acrylic acid ester that can be easily polymerized in the presence of a radical initiator, a method for producing the same, and a cured product thereof.

0002

[Prior Art] Conventionally well-known (meth)acrylic acid esters include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.
acrylate, isobutyl (meth)acrylate, 2-
Ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol diacrylate,
Examples include polyethylene glycol diacrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexaacrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and the like.

0003

[Problem to be Solved by the Invention] These (meth)acrylic esters are used in a variety of ways as ultraviolet curable resins or electron beam curable resin materials, but in both cases, the (meth)acrylic ester itself The refractive index at 20° C. is 1.404 or more, and a cured product with a refractive index of 1.404 or less cannot be obtained.

On the other hand, for example, optical fibers, which are rapidly becoming popular, can be divided into inorganic glass-based and synthetic resin-based fibers, but both types have a highly transparent core portion with a high refractive index. It consists of a low sheath (cladding). In recent years, ultraviolet curable resins have begun to be used as cladding materials due to their productivity, safety, and economical advantages, but resins that provide cured products with lower refractive indexes are now required for their performance as cladding materials. ing. In addition, in the optical field, such as holograms and various lenses that take advantage of the characteristics of high refractive index materials and low refractive index materials, there is a growing demand for ultraviolet curable resins that can produce cured products with lower refractive indexes.

[0005]

[Means for Solving the Problems] As a result of intensive research, the present inventors have found that (meth), which has been well known in the past, is particularly useful as a component of ultraviolet curable resin compositions for cladding materials of optical fibers. The present invention was completed by successfully providing a new fluorine-containing (meth)acrylic ester having a lower refractive index than that of an acrylic ester.

[0006] That is, the present invention 1 General formula (1)

[0007]

[C4]

and/or general formula (2)

0009
]

[C5]

[0010] (However, R1 is Cn F2n+1-(-
CH2 −)a −,Cn F2n+1−(−CH2
-)a-O- or H-(-CF2 CF2-)b
-(-CH2-)c-O-, R2 is H or CH3, n is an integer of 1 to 10, a is 0, 1 or 2, b is an integer of 1 to 5, and c is 0 or 1. be. )
A fluorine-containing (meth)acrylic acid ester represented by 2 General formula (3)

[0011]

[C6]

(However, R1 has the same meaning as above.) A fluorine-containing monoepoxy compound and (meth)
2. The method for producing a (meth)acrylic ester according to item 1, which comprises reacting acrylic acid. 3. A cured product of the (meth)acrylic ester described in item 1. Regarding. The (meth)acrylic acid ester of the present invention can also be used as a component of ultraviolet curable resin compositions for other optical applications by taking advantage of its low refractive properties. Furthermore, the (meth)acrylic acid ester of the present invention is
Since it is a compound having one hydroxyl group in its molecule, a new material can be provided by reacting this hydroxyl group with another compound (for example, organic polyisocyanate).

The fluorine-containing (meth)acrylic acid ester of the present invention can be obtained by reacting the fluorine-containing monoepoxy compound represented by the general formula (3) with acrylic acid or methacrylic acid. Specific examples of the compound represented by general formula (3) include 3-(perfluoro-
n-butyl)-propenoxide, 3-(perfluoro-
n-hexyl)-propenoxide, 3-(perfluoro-n-octyl)-propenoxide, 1.1-dihydroperfluoro-n-octyl glycidyl ether, 1.
1.2.2-tetrahydroperfluoro-n-octyl glycidyl ether, 2-hydroperfluoroethyl glycidyl ether,

[0014]

[C7]

[0015]

[Chemical formula 8]

[0016] etc. Examples of known catalysts used in the reaction between the compound represented by formula (3) and (meth)acrylic acid include quaternary ammonium salts such as methyltriethylammonium chloride and tetramethylammonium chloride, triphenylstibine, and triethylamine. , benzyldimethylamine, 2.4.6-tri(dimethylamino)phenol, and the like. The amount of catalyst added is 0.001 to 5.0wt to the reaction mixture.
%, particularly preferably 0.01 to 2.0 wt%.

It is preferable to use 0.9 to 5 moles of acrylic acid or methacrylic acid, particularly preferably 1 to 2 moles, per 1 mole of the compound represented by the general formula (3).

Compound represented by general formula (3) and (meth)
The reaction temperature with acrylic acid is preferably 50 to 200°C, particularly preferably 70 to 120°C. Also, the reaction time is 3
~48 hours are preferred, particularly 7 to 24 hours.

In order to prevent polymerization during the reaction, it is preferable to add a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, phenothiazine, etc. The amount added is 0.0 to the reaction mixture.
01 to 5.0 wt% is preferable, particularly 0.01 to 0.5
wt% is preferred.

The product obtained by the above reaction is usually a mixture of (meth)acrylic acid esters represented by general formula (1) and general formula (2). The (meth)acrylic acid ester of the present invention thus obtained is once dissolved in a non-aqueous solvent such as benzene, toluene, or monochlorobenzene in order to remove excess acrylic acid or methacrylic acid or a catalyst, etc., if necessary. It is often washed with aqueous alkaline solutions such as sodium hydroxide, sodium carbonate, and sodium bicarbonate. Thereafter, when the solvent is sufficiently distilled off, a (meth)acrylic acid ester containing fewer impurities and having a lower refractive index is obtained. In some cases, it may be purified by vacuum distillation or fractionated into its respective components before use.

The (meth)acrylic ester of the present invention is
A cured product is provided by a known radical curing system. For example, a known photoradical polymerization initiator such as benzophenone or 1-hydroxycyclohexylphenyl ketone is added to 0.
A cured product is obtained by adding 01 to 10 wt% and irradiating with ultraviolet rays. A cured product can also be obtained using an electron beam curing system or a peroxide curing system. The obtained cured products all have a lower refractive index than those obtained from generally known (meth)acrylic acid esters.

[0022]

[Examples] Next, the present invention will be specifically explained with reference to Examples. In the examples, parts mean parts by weight. Synthesis Examples Example 1 In a 1-liter reactor equipped with a stirrer, thermometer, and condenser, 376.0 parts of 3-(perfluoro-n-hexyl)-propenoxide, 86.5 parts of acrylic acid, 2.3 parts of tetramethylammonium chloride and 0.23 parts of hydroquinone monomethyl ether were charged and heated gradually to 9
The mixture was heated to 0 to 95°C, stirred at the same temperature for 15 hours, and then cooled to room temperature. 1500ml of toluene was added to the resulting reaction solution.
3 times with 15% sodium carbonate aqueous solution, 20%
After washing three times with brine, toluene was distilled off under reduced pressure to obtain 425.0 parts of a slightly yellow liquid. This product is a mixture of acrylic esters having the following two structures.

[0023]

[Chemical formula 9]

[0024]

[Chemical formula 10]

The refractive index of this material at 20°C is 1.
It was 3620. Further, the results of 13C-nuclear magnetic resonance (NMR) measurements of this product are shown below. The measurement was carried out by a proton decoupling method using tetramethylsilane as a reference substance and deuterated chloroform as a solvent. No. Chemical shift (pp
m) Strength 1
171.136
161 2
166.593 1942
3 165.813
563 4
132.157
5168 5
127.998 4727
6 67.
962 4814
7 63.934
3756 8
60.165
439 9
49.379 94
10 36.3
85 906 11
35.085
1738 12
34.176 5
37 13 3
3.656 1121
14 32.226
430 15
30.797
201 In addition, in addition to the above, in the range of 150 to 85 ppm, -(-CF2
-)5 - A small peak attributed to C was observed.

Example 2 Into a 1-liter reactor equipped with a stirrer, thermometer, and condenser, 276.0 parts of 3-(perfluoro-n-butyl)-propenoxide, 108.1 parts of acrylic acid, and triphenate were added. 1.9 parts of nilstibine and 0.19 parts of hydroquinone monomethyl ether were charged, gradually heated to 90 to 95°C, stirred at the same temperature for 20 hours, and then cooled to room temperature. The obtained reaction solution was dissolved in 1500 ml of toluene, and 15
After washing three times with a 20% sodium carbonate aqueous solution and three times with a 20% saline solution, toluene was distilled off under reduced pressure to obtain a slightly yellow liquid 273.
．． I got 6 copies. This product is a mixture of acrylic esters having the following two structures.

[0027]

[Chemical formula 11]

[0028]

[Chemical formula 12]

This product has the following properties. Refractive index (20°C) 1.373213C-NMR
Measurement results by NO. Chemical shift (pp
m) Strength 1
170.751
285 2
166.333 2969
3 165.554
296 4
135.146
305 5
132.027 7918
6 129.
298 547
7 127.739
7101 8
127.089
640 9 1
17.862 381
10 110.196
372 11
107.986
448 12
105.648 184
13 67.702
6812 14
64.843
465 15
63.934 5463
16 59.9
06 634 17
36.255
1471 18
34.825 307
6 19 34
．． 045 689
20 33.396
1826 21
31.836
784 22
30.407 346 Nao, 1
In addition to the above, in the range of 50 to 85 ppm, -(-CF2-)3-C which has been split into many fragments due to F coupling is present.
A small peak attributed to .

Example 3 In Example 1, 1.1.2.2-tetrahydroperfluoro-n-octylglycidyl ether 420 was used instead of 3-(perfluoro-n-hexyl)-propenoxide.
．． A slightly yellow liquid 457 was prepared in the same manner except that 0 part was used.
．． I got 6 copies. This is a mixture of acrylic esters with two productions:

[0031]

[Chemical formula 13]

[0032]

[Chemical formula 14]

This product has the following properties. Refractive index (20°C) 1.374013C-NMR
Measurement results by NO. Chemical shift (pp
m) Strength 1
171.136
300 2
166.723 4877
3 166.463
1034 4
131.637
10190 5
129.558 469
6 128.51
8 5468 7
127.218
545 8
118.123 32
5 9 113
．． 704 287
10 111.365
426 11
110.715
260 12 11
0.326 305
13 108.117
470 14
105.907
205 15
73.810 1325
16 72.510
7087 17
71.081
607 18
70.691 693
19 70.1
71 1679 20
69.781
865 21
69.132 737
9 22 65
．． 883 6283 2
3 63.804
5010 24
62.115 16
72 25 6
0.296 1202
26 46.131
192 27
34.176
834 28
33.266 2015
29 31.836
3281 30
30.407
1505 Furthermore, in addition to the above, in the range of 150 to 85 ppm, -(-CF
A small peak attributed to C of 2-)5- was observed.

Example 4 A slightly yellow colored product was prepared in the same manner as in Example 1 except that 174.0 parts of 2-hydroperfluoroethyl glycidyl ether was used instead of 3-(perfluoro-n-hexyl)-propenoxide. 234.2 parts of liquid were obtained. This product is a mixture of acrylic esters having the following two structures.

[0035]

[Chemical formula 15]

[0036]

[Chemical formula 16]

This product has the following properties. Refractive index (20°C) 1.402913C-NMR
Measurement results by NO. Chemical shift (pp
m) Strength 1
166.463
1019 2
165.944 231
3 133.326
313 4
132.027
5786 5
127.868 3610
6 117.3
43 306
7 110.585
401 8
107.856
700 9 1
04.998 387
10 91.093
407 11
72.250
848 12
67.962 4640
13 64.9
74 7839 14
62.634
668 15
61.075 9
22 16 5
9.906 355
17 33.916
246 In addition to the above, at 150 to 85 ppm, a small peak attributed to C of -(-CF2-)2-, which was split into many peaks due to coupling of F, was observed.

Example 5 In Example 1, methacrylic acid 103 was used instead of acrylic acid.
．． In the same manner except that 2 parts were used, slightly yellow liquid (30
426.0 parts (liquid at 10°C, crystallized at 10°C) were obtained. This product is a mixture of methacrylic acid esters having the following two structures.

[0039]

[Chemical formula 17]

[0040]

[Chemical formula 18]

This product has the following properties. Refractive index (20°C) 1.365013C-NMR
Measurement results by NO. Chemical shift (pp
m) Strength 1
168.023
2359 2
167.373 626
3 136.185
5642 4
129.428
354 5
126.829 7835
6 118.3
82 242
7 113.574
222 8
111.365
317 9 1
10.715 230
10 110.326
263 11
108.117
347 12
68.742 1357
13 68.222
6009 14
64.194
4243 15
36.645 1227
16 35.21
5 2375 17
33.786
1344 18
32.356 576
19 30.
927 229 2
0 18.322
3088 In addition, in addition to the above, in the range of 150 to 85 ppm, there are many fragments due to coupling of F.
A small peak attributed to C (-CF2-)5- was observed.

Examples of cured products Example 6 3 wt % of hydroxycyclohexyl phenyl ketone was added to each of the (meth)acrylic acid ester mixtures obtained in Examples 1 to 5, and coated on a glass plate to a thickness of about 50 microns. After that, it was blown for 100m using a high-pressure mercury lamp under a nitrogen atmosphere.
A cured product was obtained by irradiating ultraviolet rays at J/cm2. The refractive index of the obtained cured product is shown in Table 1.

Comparative Example The refractive index at 20°C of conventionally well-known (meth)acrylic acid esters and the refractive index of their cured products prepared in the same manner as in Example 6 are shown in Table 1. Indicated.

[0044]

[0045]

[Effects of the invention] It can be easily cured using a radical curing system, and provides a cured product with a lower refractive index than the conventionally well-known (meth)acrylate ester.
An acrylic ester was obtained.

Claims (3)

[Claims] Claim 1: General formula (1) [Formula 1] and/or General formula (2) [Formula 2] (However, R1 is Cn F2n+1-(-CH2 -)
a −, Cn F2n+1−(−CH2 − )a−O
- or H-(-CF2 CF2 -)b -(-CH
2-)c-O- and R2 is H or CH3-
and n is an integer from 1 to 10, a is 0, 1 or 2, b
is an integer from 1 to 5, and c is 0 or 1. ) Fluorine-containing (meth)acrylic acid ester. [Claim 2] A fluorine-containing monoepoxy compound represented by the general formula (3) [Claim 3] (wherein R1 has the same meaning as R1 in Claim 1) and (meth)
2. The method for producing a (meth)acrylic ester according to claim 1, which comprises reacting acrylic acid. 3. A cured product of the (meth)acrylic ester according to claim 1.