JPS58163904A - Method for producing optical transmission body of synthetic resin - Google Patents

Abstract

PURPOSE:To obtain an optical transmission body having a good index distribution efficiently in a short time by bringing monomer forming a polymer differing in refractive index from a net-like (co)polymer into contact with the transparent gel of said (co)polymer and irradiating UV rays thereto from the outside. CONSTITUTION:Polyfunctional monomers such as allyl compds. such as diallyl (iso)phthalate or the like, tetraethylene glycol dimethacrylate or the like are filled in a nylon tube or the like, whereby a transparent gel-like bar wherein the monomers are polymerized at 10-95wt% is manufactured. The bar is immersed for a specified time in a monomer forming a polymer having the refractive index larger or smaller than the refractive index that the (co)polymer pocesses and is then pulled up or while the bar is held in contact with the vapor of the monomer, UV rays are irradiated thereto from the outside. Thus the optical transmission body having the good index distribution wherein the refractive index increases or decreases gradually roughly in proportion to the square of the distance from the central axis of the bar is obtained quickly and efficiently.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of a synthetic resin optical transmission body having a refractive index distribution in which the refractive index gradually decreases or increases in approximately proportion to the square of the distance from the central axis.

This refractive index distribution in which the refractive index gradually decreases or increases is defined by the distance from the center in the radial direction being r, the refractive index at the center being no, the refractive index at the position r being n, and a positive constant A.
, B, when the refractive index gradually decreases, n=no (/--Ar2) (1) When the refractive index gradually increases, n=no (/10-Br2) (?) It is represented by a defined quadratic curve.

In Japanese Patent Application No. 7-1Ot3, a transparent gel of a reticular polymer whose polymerization has not been completed is immersed in a monomer forming a polymer having a refractive index different from that of the reticular polymer. Synthesis in which the concentration of polymeric components has a gradient that gradually decreases or increases from the surface to the inside inside the transparent gel, and then the polymerization is completed by heat treatment so that the refractive index changes continuously from the surface to the inside. A method of manufacturing a resin light buddha body is described. However, this method has the following disadvantages.

That is, the Mb layer that adheres to the outer peripheral surface of the gel object by immersion evaporates during the subsequent heat treatment step for polymerization and is extracted from the surface of the gel object or diffuses into the inside of the gel object. This causes an increase in undesirable distortion of the refractive index distribution near the outer periphery of the optical transmission body.

As a method to improve this drawback, the patent application No. 53-2792!
; is a method of manufacturing a synthetic resin transmission body whose refractive index changes continuously in approximately proportion to the square of the distance from the central axis, in which a transparent gel object is placed in an atmosphere containing vapor of the monomer Mb. A method for performing diffusion is described.

However, in this method, Mb must have a relatively high vapor pressure, for example a saturated vapor pressure higher than 3 mmHg at the temperature of contact with the gel body, since there is an optimum humidity range for the temperature at which it is diffused. Yes, there is not enough range to select Mb.

It is an object of the present invention to provide a method for efficiently manufacturing an optical transmission body that improves these conventional disadvantages and reduces distortion of the refractive index distribution near the outer periphery. This object is achieved by the present invention.

That is, the present invention provides network polymers (including copolymers) Pa
A monomer (including a monomer mixture) Ma forming the molecule (with its refractive index as Ha) is partially polymerized to form a transparent gel object, and a polymer (copolymer) having a refractive index Nb different from Na A monomer (including a monomer mixture) forming Pb (including a mixture of monomers) is diffused and double-polymerized into the transparent gel body so that the refractive index is continuously proportional to the square of the distance from the central axis. In the method of manufacturing a variable synthetic resin light transmission body, monomer Mb is contacted with the transparent gel body at an interface of the transparent gel body.
By touching it once and irradiating it with ultraviolet rays from the outside, the diffused monomer Mb is quickly polymerized, the refractive index gradient is fixed, and a good refractive index distribution is achieved up to the vicinity of the outer periphery (
This manufacturing method is characterized by being able to manufacture a synthetic resin optical transmission body (with a large effective radius).

In the present invention, the monomer Mb is brought into contact with a transparent solid object of the reticular polymer over the entire surface or part of the surface of the object. This contact is carried out, for example, by immersing the object in Mb monomer or by placing it in an atmosphere containing Mb vapor or mist droplets. This contact causes the monomer to diffuse through the contact surface of the object toward the interior of the object, so that the concentration of the monomer inside the object has a gradient that gradually decreases from the contact surface toward the inside. become. Contact between the monomer and the object is such that the monomer diffuses inside the object. If the contact temperature and time are too high, the monomer will diffuse to a uniform concentration inside the object, making it impossible to obtain a refractive index gradient. Furthermore, if the contact temperature is too high, polymerization of the monomer Mb will proceed and diffusion will become insufficient. Also,
By diffusing monomer Mb, the object having a monomer Mb concentration gradient, which already has a refractive index gradient, fixes the refractive index gradient and becomes a solvent-insoluble component to improve weather resistance. It is necessary to advance the polymerization reaction of the monomer inside the object and the network polymer of the object.

When these polymerizations are carried out by heating, it is heated to a temperature lower than the polymerization temperature, but at this time, the monomer Mb evaporates and may be extracted from the surface of the object or may be absorbed into the inside of the gel object. Diffusion also occurs at the same time, creating an undesirable distortion in the refractive index distribution near the outer periphery. However, in the present invention, since monomer Mb is diffused and the object having a concentration gradient of monomer Mb is irradiated with ultraviolet rays from the outside, monomer Mb on the surface of the object and monomer Mb inside the object are No increase in humidity occurs, and polymerization progresses more rapidly from the outside, so the monomer Mb present on the surface of the object is polymerized and fixed, and the polymerization gradually progresses to the inside. The monomer Mb concentration gradient thus obtained can be fixed as it is. That is, the polymerization can be completed without damaging the refractive index distribution near the outer periphery.

For example, an ultraviolet light source is placed relatively near the outside of the cylindrical object in which the monomer Mb is diffused, so that the light irradiation is symmetrical to the central axis of the object, in other words, the central axis of the object. The object is gradually rotated around its central axis so that the amount of light irradiation increases as it approaches the central axis, and the amount of light irradiation becomes equal in the circumferential direction of a circle centered on the central axis, or Rotating a light source around the object.

Since the portions close to the light source are irradiated with a large amount of light, the outermost portion of the object forms a polymer first, and then copolymerization progresses gradually toward the center. Furthermore, since the polymerization proceeds quickly at a relatively low temperature, evaporation and diffusion of the monomer Wb can be suppressed. A photosensitizer may be added to the monomer Mb as needed to further enhance the efficiency of polymerization.

In the present invention, the transparent solid object of the network polymer to be brought into contact with the monomer has undergone the polymerization reaction to some extent but has not yet completed, and therefore contains 10 to 95 weight parts of the component soluble in a solvent such as acetone. % must be contained.

The higher the solvent soluble component, the lower the crosslinking density of the network polymer, which increases the monomer diffusion rate.

When the content of solvent-soluble components is less than 10% by weight, it is not preferable because the monomer diffusion rate becomes low and the required contact time becomes long. Moreover, if the content of solvent-soluble components exceeds 95% by weight, it is not preferable because the polymer has difficulty maintaining its solid form.

In the present invention, Ma is a monomer having two or more allyl groups, acrylic acid groups, or vinyl groups, or having two or more groups selected from the group consisting of acid allyl groups, acryl, M l methacrylic acid groups, and vinyl groups. You can use your body. Next, the unit amount suitable for the present invention is 4,) □f
6o' (1)
Allyl compounds diallyl phthalate, diallyl isophthalate.

Diaryl esters such as diallyl terephthalate and diethylene glycol bisallyl carbonate; Triallyl esters such as triallyl trimellitate, triallyl phosphate, and triallyl phosphite; Unsaturated acid allyl esters such as allyl methacrylate and allyl acrylate f2) R1-R2R3 Both of the compounds R1 and R3 represented by are a vinyl group, an acrylic group, a vinyl ester group, or a methacrylic group. Alternatively, R1 and R
One of 3 is one of a vinyl group, an acrylic group, a methacrylic group, and a vinyl ester group, and the other is one of the other three of the above-mentioned one group.

(9) +- (more than) A group) or ■ G- ■ CH3t (CH2CH20b CH2CH2(""-0-,20
)(OH2) p (p-J~/3)(O
H2) LH (EH2Cj-CH2' (L+ 7 = '~
3) (CHg)・H (A-ON20) (Above, 2B group) (10) (3) A mixture of the monomers of (1) and (2) above, or monovinyl compounds, vinyl esters, acrylic esters and a mixture of at least seven of the three methacrylic esters and the above (1) and (2) monomers (or a mixture thereof).As Mb, X is hydrogen or a methyl group.

((EH2)j!H(J-/-za) L-propyl, b-butyl, S-butyl, t-butyl (
J-0-, Rika 1,000Hg0H20+i5(3Rg(iH3(
p-/-≦) (more than 4 (A group) or -(CF2)-Br (a-/ ~4)-OH
2(OF2)bH(b-/~za)-CH2(3H20
・(3H20F3 −(OH20H20).0F2CF2H(C=/~1I
)-(E H2CH20・OH2(OFg)aF (
a-/ ~4)-OH2(CFz)dO(OF2), g
F (d-/~ko.

! -/~l) or -3i(002H5)3 (the above IIB group) (5) CH2= (compound represented by 3HOO-R4) j4: -(OHp)f-(3F3 (f-0~
2) (the above 5A groups) or -(OH2) gH (g -/~3) (the above jB groups) (6) The above (1) as the mixture Ma of the monomers described in sections (4) and (5) ~(3), as Mb(
Any of 4) to (6) can be combined, but
In particular, if a monomer of the 2B group is used as Ma and a monomer of the 47B group or (5A) is used as Mb, an optical transmission body with extremely small chromatic aberration and excellent durability can be obtained.

In addition, to adjust the gelation state of the transparent gel object (
3) Method of adding a monomer having one unsaturated group to crosslinkable Ma and CBr41 CCl41
A method of adding a chain transfer agent such as mercaptans or a method of using both together is effective.

Next, examples of the present invention will be described.

Example 1 0.5% by weight benzoyl peroxide (B, P, 0.)
Diethylene glycol bisallyl carbonate dissolved in
) (OR-79) is filled in a Freon tube with an inner diameter of 10 mm and a length of 200 mm and heated to qo'c for gg minutes to obtain a cylindrical rod-shaped body of transparent gel. The gel contains 20.0% by weight of an acetone-insoluble component (network structure polymer).

Acetone soluble/methanol insoluble components (linear polymer)
9.0% by weight, acetone-soluble/methanol-soluble components (
It consists of 7/0% by weight of monomers or mono-decamers or trimers. Acrylic acid /, /, this rod-shaped body! ;-t3”c- in trihydroper 70 lopentyl (ZFMA)
Soak for 30 minutes. Next, around the central axis of this rod-shaped body, 7
While rotating at a speed of 0 times/min, ultraviolet rays were irradiated from a distance of 0.05 m by a Toshiba type 5HL-10 OUV lamp.

After irradiation for 1 hour, heat treatment is performed to qo''c for 21 hours.

The obtained rod-shaped body has a fixed refractive index distribution up to the periphery, and the effective radius rc - approximately p mm refractive index distribution constant A =
Approximately o, ooq, 2 mm - 2 slope t = teita.

Comparative Example/ A transparent gel solid of OR-39 prepared similarly to Example/ is soaked in gFMA at 63'C for 30 minutes.

Next, this rod-shaped body was heat treated at 0 DEG C. for 21 hours to complete the polymerization. The obtained rod-shaped body had a high refractive index at the periphery, and IrFMA was extracted during the heat treatment. Therefore, the range in which the refractive index distribution is fixed is narrow, with an effective radius re of approximately -3 mm and a refractive index distribution constant A of approximately 0.
Comparative Example 2 A transparent gel solid of CR-39 prepared in the same manner as in Example 1 was suspended in a reaction vessel heated to 70'C, and after evacuation, nitrogen gas was added. After introducing the gas, the pressure inside the reaction vessel is set to 20 mmHg.Next, FMA is injected into the reaction vessel.The amount of injection is vaporized in the reaction vessel and the FMA is deposited at the bottom of the reaction vessel.
Make sure that the amount of O liquid phase remains so that the FMA in the liquid phase does not come into contact with the transparent gel rod.

7. Continue contacting the transparent gel solid with the FMA in the gas phase;
After 20 minutes, nitrogen gas is introduced and the remaining gas phase and liquid phase fFMA are discharged, followed by heat treatment at 90'C for 2II hours. The obtained rod-shaped body was polymerized before sufficient diffusion occurred near the center, and the necessary refractive index distribution could not be obtained.

Example 2 When 5% by weight of benzoyl peroxide was added as a polymerization initiator to diallyl 7-talate and the mixture was kept at 0"C for 7 hours, a slight polymerization reaction occurred and a viscous liquid was formed.

A Teflon tube with an inner diameter of 5 Tnm and a length of 200 mm and a length of 1 m was filled with the cholera and heated at O''C for 5 hours to obtain a rod-shaped polymer with a diameter of about 3 mm. This rod-shaped gel contained tIz% by weight of acetone-insoluble components. This rod-shaped body is immersed in methyl methacrylate at 70"C for 20 minutes. Next, the rod-shaped body taken out from the core of methyl methacrylate is rotated around the central axis at a speed of 10 times/min while being exposed to ultraviolet rays. After 7 hours of irradiation, the mixture is heated for 241 hours to complete the polymerization of methyl methacrylate and diallyl phthalate.

The obtained rod-shaped body has a fixed refractive index distribution up to the periphery, and has an effective radius re of approximately 2 mm and a refractive index distribution constant A-0-
0/2'l mm"(1':)Gradient' with 1."C ita.

) Example 3 0.3% azoisobutyroni in diallyl isophthalate)
Add IJ and heat to 10"C for 20 hours to make a diameter of about 3 m.
The diallyl isophthalate polymer obtained by cast molding into a rod shape of m 2 had an acetone-insoluble component of 110.3% by weight. This rod was placed in methyl methacrylate for 70'
C-Soak for 20 minutes. Next, the rod-shaped body taken out from methyl methacrylate is irradiated with ultraviolet rays while rotating at a speed of IO times/minute around the central axis. After irradiation for 90 minutes, the polymerization is completed by heating to go''c for 2 hours. let

The obtained rod-shaped body has a fixed refractive index distribution up to the periphery, and has an effective radius rc - approximately /, /! ; mm refractive index distribution constant A=approximately o:olI da mm-2.

Example 1 A Teflon tube with an inner diameter of s'' and a length of 200 mm was filled with diethylene glycol bisallyl carbonate in which 15% by weight of benzoyl peroxide was dissolved.
Humidify for 90 minutes to obtain a transparent gel rod. The gel contained 2% by weight of components insoluble in acetone. This rod-shaped body is immersed in styrene at 60°C for 30 minutes. Next, the rod-shaped body is irradiated with ultraviolet rays while being rotated around the central axis at a speed of IO times/minute. After 7 hours of irradiation, 100″C
Heat treated for 20 hours. The obtained rod-shaped body has a fixed refractive index distribution up to the periphery, and an effective radius r (H = approximately 2 mm
The refractive index distribution constant B had a slope of −0.03 mm −2 .

Example: 0.1 part of carbon tetrabromide and o and i parts of benzoyl peroxide were dissolved in 100 parts of tetraethylene glycol dimethacrylate, and the inner diameter was 3. A cylindrical rod-shaped body of transparent gel is obtained by filling a Teflon tube formed to a diameter of /1 mm and processing it in SO''C for 10 minutes.The gel is an acetone-insoluble component.23.
2% by weight, acetone soluble/methanol insoluble component 0.3
The methanol-soluble components were 7L and 31'% by weight.

The above-mentioned transparent gel rod is suspended in a reaction vessel heated to 30°C, and after evacuation and introduction of nitrogen gas, the pressure inside the reaction vessel is set to 10 mmHg (absolute pressure).

22.2-trifloethyl methacrylate (JFMA) in which o, oos weight percent of hydroquinone is dissolved is injected into the reaction vessel. Adjust the amount of rI and add J to the bottom of the reaction vessel.
Allow FMAO liquid phase to form.

Next, while rotating the transparent gel rod around the central axis at a speed of 1S times/min, the Toshiba 5HL-
Irradiate ultraviolet light with a 10 OUV lamp. At this time, at the bottom of the reaction vessel, ? Avoid exposing the FMA liquid phase to ultraviolet light. After 3 hours, nitrogen gas was introduced and remained. ? F
After discharging the MA, it is heat-treated for 2II hours to go''c.The obtained rod-like body has a refractive index distribution of the formula (1) with radius /, up to the wing range, and the refractive index distribution constant is =0
．． 02 gua mm-2.

(/9) Procedural Amendment April 1980 2?1] Patent Application No. 3 Otsu No. 4/1979 2 Name of Invention Method for manufacturing a synthetic resin optical transmission body 3 Relationship with the person making the amendment Patent Applicant address Address: G-chome, Doshomachi, Higashi-ku, Osaka-shi, Osaka Prefecture Name:
vtoo) Nippon Sheet Glass Co., Ltd. Representative Suga Shun Numa
Hiko (and 1 other person) Agent address: Shinbashi Sumitomo Building S, No. 3 Shinbashi S-chome, Minato-ku, Tokyo Date of amendment order 7 Contents of amendment (]) "Low" in line g, page 2 of the statement (2) On page 11 of the specification, correct the line 1 acrylic acid to 1 methacrylic acid.

(3) Supplement the power of attorney as shown in the attached document.

that's all

Claims (1)

[Claims] Monomers (including monomer mixtures) forming network polymers (including copolymers) Pa (with Na as its refractive index)
A transparent gel object is formed by partially polymerizing Ma, and a monomer (including a monomer mixture) Mb forming a polymer (including a copolymer) pb having a refractive index Nb different from that of Ha is used as the transparent gel object. In a method for producing a synthetic resin optical transmitter whose refractive index changes continuously in approximately proportion to the square of the distance from the central axis by contacting the surface of the monomer Mb and polymerizing it by diffusion into the interior thereof, the monomer Mb A synthetic resin light transmitting body that has a good refractive index distribution up to the vicinity of the outer periphery by rapidly polymerizing the monomer Mb that diffuses by irradiating ultraviolet rays from the outside to a transparent gel object that has been brought into contact with or is being brought into contact with. manufacturing method.