JPS61275331A - Optical crosslinked siloxane polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to crosslinked siloxane polymers, and more particularly to crosslinked siloxane polymers having substituents for controlling refractive index.

[Prior Art] Glass has been widely used as an optical material since ancient times, and there are a wide variety of types with respect to refractive index, dispersion value, etc. However, since all glasses have a large refractive index, there are no known materials with low refractive index and high dispersion. In addition, glass materials have poor workability and lack flexibility in shape, making it difficult to manufacture asymmetric lenses and the resulting products are expensive.

Plastic is a relatively inexpensive optical material, but there are only four to five types of materials that can be used, and plastic has poor heat resistance.

Siloxane polymers are attracting attention as interesting optical materials because they have excellent transparency and heat resistance, and exhibit rubber-like elasticity after crosslinking and curing.

In the past, for example, U.S. Patent No. 3,228,741 (1
(January 11, 1996) discloses a contact lens made of transparent silicone rubber with good gas permeability.

U.S. Patent No. 3,996,189 (December 7, 1976)
In order to match the refractive index of the silica filler and the refractive index of the siloxane polymer, we used an appropriate amount of a siloxane polymer containing phenyl groups to match the refractive index of the siloxane polymer in the composition with the refractive index of the siloxane polymer. A method of index matching and thereby making optically transparent siloxane polymers is disclosed. That is, a siloxane polymer having vinyl groups at both ends, both containing 6 to 16 mol% of phenyl groups, and a siloxane polymer having hydrogen-silicon bonds (=SiH) at both ends are subjected to an addition reaction (hydrosilylation reaction) using a platinum catalyst. ) to obtain an optically transparent crosslinked siloxane polymer.

Next, the viscosity at 25°C is 100-15,000c.
Siloxane polymer containing phenyl groups with vinyl groups blocked at both ends of P (molar ratio of methyl groups/phenyl groups 1/! ~
10/1) and the viscosity at 25°C is 0.5 to 5.0OO
JP-A-55-130844 discloses a coating material for optical communication glass fiber [cladding material (having a higher refractive index than the core material)] consisting of a siloxane polymer having silicon-hydrogen bonds (SiH), which is CP, and a platinum compound. (Released on October 11, 1980).

On the other hand, U.S. Patent No. 3,341,490 (October 1967)
12), transparent siloxane polymers mixed with reinforcing silica-based fillers are obtained primarily by blending dimethyl/phenylmethylsiloxane copolymers and dimethyl/methylvinylsiloxane copolymers.

It relates to bridged siloxane polymers, in which the refractive index is controlled by a phenyl group-containing siloxane. Specific methods include 1,3.5-trimethyl-1,3,5-triphenyloncrotrisiloxane, 1,3,5.7-titramethyl-1.3.5.7-
using a phenyl group-containing cyclic siloxane monomer such as titraphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotrisiloxane, and a vinyl group for crosslinking by addition reaction;
It is a siloxane polymer obtained by crosslinking polymers such as dimethyl/diphenylsiloxane copolymer, dimethyl/methylvinylsiloxane copolymer, methylphenylsiloxane polymer, etc. or blends thereof into which silicon-hydrogen bonds have been introduced through an addition reaction.

The above conventional techniques have the following drawbacks.

1) Since the refractive index is mainly controlled by phenyl groups, the range of refractive index control is limited.

2) In order to precisely control the refractive index by copolymerizing a phenyl group-containing siloxane monomer, it is necessary to repeat several trial productions starting from the copolymerization process, which is uneconomical and time-consuming. Ru.

3) If you want to obtain several types of crosslinked siloxane polymers with different refractive indexes, it is necessary to perform copolymerization with different amounts of phenyl group-containing siloxane polymer for each type, which causes various problems in terms of quality control, inventory, etc. This will cause some inconvenience.

4) Refractive index control using polymer blends is limited by the compatibility of both polymers, and even if compatible polymers are used, Rayleigh scattering will increase.
Transparency is compromised.

Further, all of the above-mentioned known techniques relate to optically transparent siloxane polymers, and are intended for use in contact lenses, etc., and do not attempt to precisely control the refractive index. Technology to control the refractive index, which is the basic principle of optical transmission lines, optical fibers, lenses, etc., is important. In addition, in order to obtain good light transmission characteristics, it is necessary to match the refractive index between materials or elements, and this requires precise control of the refractive index.

OBJECT OF THE INVENTION] One object of the present invention is to provide an optical crosslinked siloxane polymer having a substituent that can freely and largely change the refractive index.

Another object of the present invention is to provide an optical crosslinked siloxane polymer having a substituent for controlling the refractive index without synthesizing and polymerizing a siloxane monomer having such a substituent.

Another object of the present invention is to introduce substituents into siloxane polymers to control the refractive index.

In both cases, crosslinking of the siloxane polymer is also progressed to obtain a crosslinked siloxane polymer for optical use.

[Structure of the Invention] These objects of the present invention are: (a) a siloxane compound or silane compound having at least one silicon hydride and having a substituent for controlling the refractive index;
b) By a hydrosilylation reaction with a siloxane polymer having a non-conjugated unsaturated bond, the siloxane polymer with the substituent introduced into the side chain is converted into a non-conjugated type in the siloxane polymer that remains unreacted in the hydrosilylation reaction. This is achieved by an optical crosslinked siloxane polymer characterized in that it is crosslinked via an unsaturated bond by a hydrosilylation reaction with (c) a siloxane compound or a silane compound having at least two silicon hydrides.

Siloxane polymer (b) with non-military unsaturated bonds
For example, the formula: [wherein R' is a substituent having a non-conjugated unsaturated bond, R
2, R3 and R4 are the same or different carbon numbers 1-12
an alkyl group or an alkoxy group, X and y represent positive integers. ] It is a compound shown by.

Examples of the substituent having a non-conjugated unsaturated bond include a vinyl group, allyl group, and isopropenyl group.As the alkyl group, a lower alkyl group such as a methyl group and an ethyl group, particularly a methyl group, is preferable. As the alkoxy group, lower alkoxy groups such as methoxy and ethoxy are preferred.

Further, both ends are preferably blocked with a substituent having a non-conjugated unsaturated bond such as a vinyl group.

Among the silicon hydride-containing silane compounds of (a), those having a substituent for controlling the refractive index include phenyldimethylsilane, diphenylmedylsilane, phenylsilane, diphenylsilane, methylphenylsilane, p
-bis(dimethylsilyl)benzene, triphenylsilane, bis[(p-dimethylsilyl)phenylconythyl, cyclohexyldimethylsilane and the like.

Examples of (a) siloxane compounds having silicon hydride having a substituent for controlling the refractive index include 1.
In addition to low molecular weight ones such as 3-diphenyl-1,3-dimethylsiloxane, the following siloxane polymers may be used.

That is, by a hydrosilylation reaction between a siloxane polymer having silicon hydride and an organic compound having at least one non-conjugated unsaturated bond and having a substituent for controlling the refractive index, the side chains of the siloxane polymer are A siloxane polymer having the substituent introduced therein may also be used.

Examples of the siloxane polymer having silicon hydride include the formula: [wherein R1' is hydrogen or an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and R@ and R7 are the same or different alkyl groups having 1 to 12 carbon atoms] or an alkoxy group,
X and y represent positive integers. This is a compound shown by .

Also in compound (n), the alkyl group is preferably a lower alkyl group such as methyl or ethyl, particularly a methyl group. As the alkoxy group, lower alkoxy groups such as methoxy and ethoxy are preferred.

Substituents for controlling the refractive index include aromatic hydrocarbon groups or fluorine-containing hydrocarbon groups, such as aromatic hydrocarbon groups such as phenyl, naphthyl, anthryl, and pyrenyl groups, fluorine-substituted Alkyl groups (eg, trifluoropropyl group) are preferred.

Various organic compounds can be used as the organic compound having at least one non-conjugated unsaturated bond and a substituent for controlling the refractive index, for example, the formula: %Formula% [wherein R@, RQ , RIG and R'' represent the same or different substituents, and at least one represents a substituent for controlling the refractive index.

The hydrosilylation reaction in this case proceeds, for example, as shown in the diagram below.

R8RI O → ～between～Si Si～milcy
H R"-C-R" - RIOCR11 Through this reaction, a substituent for controlling the refractive index can be introduced into the side chain of the siloxane polymer having silicon hydride bonds, and some of the silicon hydride bonds is left unreacted.

The above has at least one silicon hydride of (a),
In addition, a silane compound or a siloxane compound having a substituent for controlling the refractive index was described.

The hydrosilylation reaction between the siloxane polymer having a non-military unsaturated bond (b) and the siloxane compound or silane compound having a substituent for controlling the refractive index and silicon hydride (a) is performed using shi÷I]τrs
71/A! +nS meeting - 1SiI-2, S
I ”/to, 2, -9 i^to -+ llSi mi fC
1l = Cl1t CH= Cl1t C
1l = C11y→ MANS i ＾Heli Sea Si
^~Yashishi St Hehachi~-CHt CH=
CHt CHtl CH2CH2 1,1 Si=r 5iEf Here, "represents a chemical structure containing a substituent for controlling the refractive index. Through the hydrosilylation reaction shown in the above figure, a siloxane polymer having non-conjugated unsaturated bonds is formed. A substituent for controlling the refractive index can be introduced into the side chain.

Next, the siloxane compound or silane compound (c) having at least two silicon hydrides and the siloxane polymer having a non-conjugated unsaturated bond remaining unreacted are crosslinked by a human-rosilylation reaction, for example, as follows. Proceed as follows.

FF F -A/S i A/W-S i M#S i~~^
Pigeon H2 Ht → Si Si CN3 Ht ■Kazu~Si^~suSt^~-9t^-^~l
] F F Here, F represents a chemical structure containing a substituent for controlling the refractive index introduced into the side chain by a hydrosilylation reaction.

Crosslinking may be carried out after the completion of the hydrosilylation reaction between the siloxane compound or silane compound (a) and the siloxane polymer (b), or during the hydrosilylation reaction, the siloxane compound or silane compound (c) may be present to form both hydrosilyls. The reaction may be carried out competitively.

Silane compounds with at least two silicon hydrides (
Examples of c) include dimethylsilane, methylsilane, and tetrakis(dimethylsiloxy)silane. Further, as long as it has at least two silicon hydrides, it may be selected from the silane compounds listed above as the silane compound (a) having a substituent for controlling the refractive index.

The siloxane compound (c) having at least two silicon hydrides may be a siloxane polymer represented by formula (II) in addition to 1,1,3,3-tetramethyldisiloxane. Further, as long as it has at least two silicon hydrides, it may be selected from the siloxane polymers exemplified as the siloxane compound (a) having a substituent for controlling the refractive index.

Usually, it has a siloxane compound or silane compound (c) having at least two silicon hydride bonds mainly for crosslinking, a substituent for controlling the refractive index, and at least one silicon hydride bond. Use of a siloxane compound or a silane compound (a) in combination provides preferable results from the viewpoint of both refractive index control and elastic modulus (network density) control.

However, as long as there are two or more silicon hydride bonds, the siloxane compound (a) and the silane compound (a) may be the same as the siloxane compound (c) and the silane compound (c).

[Effects of the Invention] According to the present invention, any substituent can be introduced into the siloxane polymer by a hydrosilylation reaction.
The refractive index of the siloxane polymer can be controlled arbitrarily.

f nf1 day L-1-+l1-F shi +-TFR
7 = even f m 1 hl 4 - h 2 k-s J, nz It is possible to introduce a substituent into a siloxane polymer and also to proceed with crosslinking of the siloxane polymer, easily obtaining an optical crosslinked siloxane polymer with a different refractive index. be able to.

Because of the above effects, it is necessary to match the refractive index between materials or elements in order to obtain good light transmission characteristics, such as guiding waveguides, optical fibers and their joints, etc.
It can be used for branch parts, lenses, junctions with optical elements, etc.

Examples Example 1 (Mv=62400, k=19.3%, nr)! 0=
1.413) 2,0 g.

(Mw=4700, m=32.2%, nDtO=1.402) 1.0g1 phenyldimethylsilane1. Og, isopropyl alcohol solution of chloroplatinic acid (3,8X 10-3
M) 0, 1 m (He) was thoroughly mixed and reacted at 70°C for 1 hour to obtain a transparent crosslinked cured product.The refractive index of this cured product at 20°C was measured to be 1.421. there were.

Example 2 2.0 g of polymer (1) used in Example 1.

(Mvt-6000, p=42.2%, q=25.6%
, nD" = 1, 501) t, o g, phenyldimethylsilane lOg, isopropyl alcohol solution of chloroplatinic acid (34X10-3
M)0, 1 m (l) were mixed well and reacted at 70°C for 1 hour to obtain a transparent crosslinked cured product.The refractive index of this cured product at 20°C was measured and was found to be 1.429. there were.

Example 3 (Mat= 132200.5=24.2%, n,”=
1.416) 2,0 g, phenylsilane 0,9 g, isopropyl chloroplatinic acid 7) Lt:I-/Iz solution C3,
8x 1G-3M) 0, 1 m (mix 1 well,
As a result of reacting at 100° C. for 1 hour, a slightly cloudy crosslinked cured product was obtained. The refractive index of this cured product at 20° C. was measured and found to be 1.437.

Example 4 5.0 g of poly v-(2) used in Example 1, CHt=C
HC, Ps 1. 0.1 mQ of an isopropyl alcohol solution (3.8 x 10 -3 M) of Og and chloroplatinic acid were mixed well and subjected to a hydrosilylation reaction at 50° C. for 3 hours in an ampoule. The product was precipitated with methanol, collected and dried. Next, 0°2 g of this obtained liquid material was added to the N1d
fJL'Tahoe')mer (J) 1.0g, isopropyl alcohol solution of chloroplatinic acid (3,8x10-3M) 0
．． 05mC was mixed well and subjected to hydrosilylation reaction at 50'C for 3 hours. Furthermore, this one has 1.1, 3.3
-Add 0.05g of tetramethyldisiloxane and 70℃
As a result of reacting for 1 hour, a transparent crosslinked cured product was obtained. When the refractive index of this cured product at 20'C was measured, it was found to be 1.
It was 403.

Example 5 2.5 g of polymer (2) used in Example 1, 0.5 g of 9-vinylanthracene, 3 II la of toluene, isopropyl alcohol solution of chloroplatinic acid (3,8 x 10-
"M) 0.05m12 well mixed, 50ml in ampoule
The mixture was subjected to a hydrosilylation reaction at ℃ for 3 hours. The product was precipitated with methanol, collected and dried.

Next, 0.1 g of the obtained liquid material was added to 1.0 g of the polymer (1) used in Example 1. Og, the polymer used in Example 1 (
2) 0.0, 1 g and 0.05 m4 of isopropyl alcohol solution of chloroplatinic acid (3.8 x 10 -3 M) were mixed well and reacted at 70°C for 1 hour to obtain a transparent crosslinked cured product. The refractive index of this cured product at 20°C was measured and found to be 1.416.

Claims (1)

[Claims] 1. (a) a siloxane compound or silane compound having at least one silicon hydride and a substituent for controlling the refractive index; and (b) a non-conjugated unsaturated bond. (c) A crosslinked siloxane polymer for optical use, which is crosslinked by a hydrosilylation reaction with a siloxane compound or a silane compound having at least two silicon hydrides. 2. The siloxane compound (a) is produced by a hydrosilylation reaction between a siloxane polymer having silicon hydride and an organic compound having at least one non-conjugated unsaturated bond and having a substituent for controlling the refractive index. The optical crosslinked siloxane polymer according to claim 1, which is a siloxane polymer in which the substituent is introduced into the side chain of the siloxane polymer. 3. The siloxane compound (c) is formed by a hydrosilylation reaction between a siloxane polymer having silicon hydride and an organic compound having at least one non-conjugated unsaturated bond and having a substituent for controlling the refractive index. The optical crosslinked siloxane polymer according to claim 1 or 2, which is a siloxane polymer having the substituent introduced into the side chain of the siloxane polymer. 4. The optical crosslinked siloxane polymer according to any one of claims 1 to 3, wherein the substituent for controlling the refractive index is an aromatic hydrocarbon group. 5. The optical crosslinked siloxane polymer according to any one of claims 1 to 3, wherein the substituent for controlling the refractive index is a fluorine-containing hydrocarbon group. 6. The optical system according to any one of claims 1 to 5, wherein the siloxane compound or silane compound (c) has at least two silicon hydrides and has a substituent for controlling the refractive index. Crosslinked siloxane polymer for use. 7. The optical crosslinked siloxane polymer according to claims 1 to 6, wherein the siloxane compound or silane compound (a) and the siloxane compound or silane compound (c) are the same compound.