JPS6070403A - Production of near parabolic plastic body - Google Patents

Abstract

PURPOSE:To obtain relatively easily a polymer having an intended refractive index distribution by dipping a circular columnar transparent polymer contg. an epoxy group into a specific swellable liquid to swell said polymer then dipping the polymer into a reactive liquid to diffuse the lower molecular compd. into the polymer and to cause both to react and drying the polymer. CONSTITUTION:A circular cylindrical transparent polymer contg. an epoxy group is dipped in a swellable liquid which satisfies 1.1<=V/V0<=3.0 so as to be swollen up to prescribed volume. V0 in the formula is the volume of the polymer prior to dipping in the swellable liquid and V is the volume of the polymer when the polymer is dipped and swollen in said liquid with the specified content of the liquid in the polymer. The polymer is thereafter dipped successively into >=2 kinds of reactive liquids contg. lower molecular compds. which have reactivity with an epoxy group and form a polymer having the refractive index lower than the refractive index of the above-mentioned polymer at different contents from the liquid having the lower concn. of the lower molecular compd. to the liquid having the higher concn. to diffuse the lower molecular compd. into the polymer and to cause both to react then the polymer is dried, by which the near parabolic plastic having high productivity and excellent bendability is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an improved light-focusing synthetic resin body.

As a focusing light transmitter, a glass fiber body whose refractive index gradually decreases from the entire central axis toward the table WI has already been proposed in Japanese Patent Publication No. 4 (?-ElA). The problem with optical transmission bodies is that they have low productivity, are sold at market prices, and have poor flexibility.
r has.

A method has been proposed in which a converging light transmitting body made of synthetic polymer is used as a shield for such a converging light transmitting body made of glass, which is highly productive and has a vague flexibility. . These composite value 11t4-equipped focusing transmitters can be roughly divided into: (1) The remaining ions are continuously changed by L degrees from the central axis of the synthetic resin body made of ion merging toward the surface. All can be L (Special Public Sho Daku No. 2491.3), (ko)
Jail A synthetic resin body manufactured from a mixture of two or more kinds of 6 types of polymers with different ratios is treated with a specific solvent,
? A product produced by partially dissolving and removing at least one of the constituent components of the synthetic citron fat (Japanese Patent Publication No. 28039), (3) A polymerization method using two monomers with different refractive indexes. (Tokukosho!; 'l-, 3030/issue) - (da) From the surface of the crosslinked polymer, from the surface of the polymer. A monomer with a low refractive index is diffused and arranged so that the content of the monomer changes continuously from Table m1, and then polymerized to give a refractive index distribution (Sho Kosho 32'-3837) , Sustainability 11dst-, Ytsx No. 1], and (1) A low-molecular compound having a refractive index lower than that of the polymer is diffused and reacted with the surface of the polymer to create a continuous refractive index distribution from the surface to the inside. (Tokusho S Kuko qt, g2@) etc. Among these, (1
) ~ (lI) methods are: - It is difficult to manufacture an optical transmission body with a high light focusing property, it is extremely difficult to select manufacturing conditions to improve the light focusing property, or it happens that the light focusing property is low. Each of these manufacturing methods has its own problems as an industrial technology, such as not necessarily achieving reproducibility even if conditions are found. Compared to these methods (1) to ('l),
The method (S) has the advantage that the thermal constant width S of the conditions for forming the refractive index distribution is wide and that it can be obtained with relatively good reproducibility.

However, the manufacturing conditions described in this publication tlJJ, that is, the anti-1 + j\ East coalescence is directly immersed in a reactant with a refractive index lower than that of the undercarriage body, or in a diluted bath solution of the anti-16 product. Bandai described the spreading motion of low-molecular substances into the chassis body as a method to solve this problem, which often does not match the formation conditions of the yC-focusing distribution. Because there are many conditions to set for the optimum flexural index distribution, the selection of conditions is extremely difficult in the method of changing the temperature and intensity of the processing bath with time. In order to solve the problems in forming the refractive index distribution, the inventors of the present invention have made extensive studies, and by applying the method shown below, it is relatively easy to create a weight having the desired refractive index distribution. The present invention was completed by discovering that coalescence can be obtained.

In other words, the gist of the present invention is to immerse a cylindrical transparent epoxy group-containing "swelling part that fully satisfies formula (1)" in a liquid that swells to a predetermined volume. , the content of a low-molecular compound that is reactive with an epoxy group and that reacts to produce a polymer having a refractive index lower than that of the polymer is different (concentration of the VC compound in the reaction solution). 1 molecular compound is immersed in sequence from the exhaled liquid to high quality (coalescence 1) light characterized by diffusing and reacting into 4 parts, and then drying) □ ■ ll≦−≦j, 0 (1) ■0 [In the formula, ■o is the volume of the polymer before being immersed in the 1N liquid, and ■ is the volume of the liquid in the polymer in the liquid. It shows the volume of the polymer when it is swollen and immersed until the content becomes constant at GJ.] What is the volume (V) of the polymer at which the liquid content in the polymer becomes 1 Bo? , υCylindrical shape after ura■ 1 Swelling degree of the polymer (te) is within S% per lz and within the υ variation range, and when visually observed, there is an expansion of liquid in the polymer. There is no boundary surface associated with 'li, and the volume in the filtration is reduced so that equilibrium swelling occurs.

In this way, by pre-dispersing the conjugate before diluting the low-molecular-weight compound, it is now possible to easily form a refractive index distribution that exhibits light focusing properties. (The degree of swelling is set to 1i in the next step.
J1 Sazeru Molecule Transformation Iyubi 1 Naru no Takano J, '14, Line has a close relationship with molecular size. Molecules with large molecular size are 410 bodies of swelling phase 1 of diffusion, reaction + ji] Is it necessary to make it bigger?

If a cylindrical transparent polymer containing an epoxy group is immersed into a swollen throat body, the degree of swelling (1) is /l.
If it is smaller than 0, it will be absorbed into the polymer when it is immersed in a diluted solution containing a low molecular weight compound that is reactive with epoxy groups and has a lower refractive index than the polymer. Not only does the diffusion rate of low-molecular-weight compounds become too low, productivity drops significantly, but
Reaction occurs preferentially at the polymer surface layer, making it difficult to form a refractive index distribution that continuously changes from the surface toward the center, which is necessary for image transmission.

10,000, If the degree of swelling (-) when the cylindrical transparent chassis body containing epoxy groups is immersed in a liquid is larger than 3θ, the degree of swelling becomes too large and the refractive index After forming the distribution, when drying the chassis,
Stretching due to chalk may occur, wrinkles on the surface tm+ may occur due to shrinkage, and depending on the conditions, the underbody may become white or crack.□Therefore, when the underbody is immersed in liquid to swell. , 1141 degrees need to be set within a range that satisfies equation (1).

In addition, a cylindrical transparent body body containing an epoxy group swollen to the extent that formula (1) is added is reactive with the epoxy group, and is reacted with a bending height lower than that of the body body. When immersing a car body with a low molecular weight in a dilute solution containing a low molecular weight compound and causing a reaction with the low molecular weight compound, as the low molecular weight compound reacts with the epoxy group, the reaction near the surface layer of the cylinder increases. , the amount of epoxy groups involved in the reaction decreases, for example, in Applied Optics (AppliθdQp
tics) / Vol. 9, p. 1099 (iqgθ year), the slope of the refractive index distribution from the theoretical refractive index distribution formula for a Rondo-shaped lens becomes large near the surface layer of the Rondo, and the curve between the center of the Rondo and the surface layer of the Rondo This results in a difference in light focusing performance between the two, resulting in a decrease in light focusing performance.

In order to completely prevent such a decrease in light focusing performance, the decrease in reaction probability due to the decrease in residual epoxy groups in the surface layer as the reaction progresses is compensated for by increasing the concentration of low-molecular reactants. There is a need. For this purpose, at least 2
After creating reaction blocks with different concentrations of low-molecular-weight reactants, and immersing the swollen cylindrical car chassis in low-concentration baths of low-molecular-weight compounds for an appropriate period of time, they were sequentially exposed to high-concentration baths. A reaction method involving transitional immersion is required.

Naturally, the present invention also includes six methods in which the concentration of the low molecular weight reactant is not increased continuously or sequentially as the reaction progresses.

Specific examples of the transparent chassis body containing an epoxy group used in the present invention include glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate,
At least one monomer of β-methylglycidyl methacrylate and other monomers, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, styrene, α-methylstyrene, trifluoro Co-Together with ethyl methacrylate, hexafluoroisopropyl methacrylate, pentafluoropropyl methacrylate, ethylene glyfur dimethacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, etc.
Alternatively, a homopolymer of glycidyl methacrylate or β-methylglycidyl methacrylate may be mentioned. Among these, polymers containing β-methylglycidyl methacrylate as the main component have relatively good thermal stability of the epoxy group, high transparency, and a relatively high secondary transition point (about 75C). Therefore, it is the most preferable.

The number of epoxy groups contained in the polymer is not limited to the number of rows, but it is related to the difference in the curvature of the ar index between the surface of the vehicle body and the center, and is related to the size of the aperture. The rt of the epoxy group-containing monomer is 70% by mole of the molten carbon contained in the coalescence.
If it is less than mol%, the transmitted light storm will be low and only a small field of view can be obtained. Therefore, from a practical standpoint, it is preferable that the epoxy group-containing monomer is contained in the polymer in an amount of 10 mol % or more.

The cylindrical transparent composite material containing the epoxy base used in the present invention is prepared by a lump binding method. The method for shaping into a cylinder is to place a mixture of a monomer or a partially polymerized product and a polymerization initiator in a cylindrical container whose inner diameter is as uniform as possible and whose roundness is maintained. Cutting resin sheet metal produced by injection polymerization method using heat or light, or cast polymerization method using two tempered glass plates,
An example is a method of machining into a cylindrical shape. Suitable examples of the cylindrical container include a glass tube with improved peelability, a cylindrical tube made of polypropylene or polyethylene, and a cylindrical tube made of polytetrafluoroethylene. The inner diameter of the cylindrical tube is suitable for the cylindrical transparent polymer used in the present invention. As a polymerization initiator, 1 m M 44 of thermal polymerization using electricity, for example,
Examples include azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, and Kotogane initiators such as benzoin alkyl ether.
Two or more polymerization initiators may be used in combination. In addition, when producing a cylindrical transparent polymer bar, a method for minimizing Vr-generated air bubbles in the polymer is to use a partially polymerized product and change the polymerization temperature over time under pressure. However, the yen f! Polymerization conditions must be appropriately selected depending on the type and size of the tube.

Specific examples of corrugated bodies used in the epoxy group-containing monomer pork oil used in the present invention include methanol, ethanol, propatool, ethylene glycol, and their alcohols, methyl acetate, ethyl acetate, and methyl ether. Examples include, but are not limited to, mixed solvents of ketones, tyral, anisole, ethylene glycol dimethyl ether, etc., and ethyl ether, propyl ether, butyl ether, etc.

Specific examples of low-molecular compounds having reactivity with the epoxy groups used in the present invention and having a refractive index lower than that of the polymer are shown by general formulas (1) to (IV) in F. fluorinated carboxylic acid represented by the general formula [■] ~ [■], and the general formula (IX) ~ [■]
Examples include fluorinated alcohols shown in the following.

C,F,n+,C0OH(I) CnF,, +, CH,C0OH(n)1((CF,
CF2)mCOO)l (m)H(CF2CF2 J
CH,C0OH(IV)CnF,+1CH101([
■] H (OF, CF2). CH,Of((X)I((CF
, CF2), Cf(,CH,OH(XI)CkF,
+, CH2CH20HC, XI [] (general formula [I] ~
In [■], n is an integer of / -If, m is the number of copies of l-da, AG; i / is an integer of ~3, and k &I / is a severance of ~. ) The reaction method between the compounds represented by the general formulas CI3 to [■] and the cylindrical Demei Higashi compound containing an engineered group is at least 4! I (Create a reaction solution with a concentration of a low-molecular-weight compound with a gradient of 100%, and then react in the reaction solution with a low concentration for an appropriate period of time. In this case, there is a relationship between the diffusion reactivity of low molecular weight compounds into the fishing rod, the temperature of the reaction solution, and the degree of swelling of the polymer, and these effects must be taken into consideration when determining its value. There is.

If the integers n and m shown in the general formula [I] ~ [notification].

If the values of 1 and 2 exceed S and DA+J+gt, respectively, the molecular size becomes too large, so the swollen polymer (P), which creates a continuous temperature gradient essential for image transmission, is
1 will cause significant damage. Therefore n1m, 1
．． The value of is S, Da.

, 3. A low-molecular compound having the general formula [■] to [ ■] In the case of fluorinated alcohols shown in
Chapter [Published by Detsukasha]
ESINS” Chemistry and 'l'e
chronology edited by ('1ayton
A, May and Yoshio Tanaka.

Basic catalysts such as gold alkoxides and tertiary amines as described in DEKKERINC, ), or acids such as sulfuric acid, boron trifluoride ethyl ether complex, boron trifluoride methanol complex, and carboxylic acids. A method in which a catalyst is used in combination to carry out the reaction is preferred.

Specific examples of diluents used when reacting compounds represented by general formulas [■] to [■] with polymers include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glyfur, anisole, Preferred examples include ethylene glycol dimethyl ether and mixtures thereof with ethyl ether, propyl ether, butyl ether, etc., but are not limited to these.

After disposing a low-molecular-weight compound having anti-b6 properties with epoxy groups with a continuous concentration gradient from the surface of the cylindrical polymer toward the center, when the polymer is taken out of the reaction tank and dried, the reaction solution is After pre-drying under conditions that do not exceed the boiling point of the diluent plus 10Cf, then 1.20~/30
7): It is preferable to carry out a two-stage drying method in which the bundle is dried at a temperature in the range of 2 to 30% until almost no diluent remains in the combined bundle. The reason for this is that air bubbles may be generated in the pure coalescence due to rapid heating at high temperatures. In addition, depending on the case, remove reaction nests and dry fish (you may replace the bath agent with a low Δ peak point bath agent and dry it after L).

The C-agglutinating synthetic or persimmon fat bodies produced in this manner are cut into various lengths and the cut surfaces are polished before use.

The light-focusing synthetic sacroiliac according to the present invention is a Rondo lens used in a multi-Ifi-Tawarada lens array, an optical fiber coupling element, a yC splitter, a line sensor, etc.
1. The present invention is expected to be used in a wide range of applications, such as type optical fibers.Hereinafter, the present invention will be explained in more detail with reference to Examples.

The production of the transparent polymer and evaluation of swelling degree and light concentrating performance were carried out as follows.

(1) Creation of cylindrical Nishimei polymer containing epoxy groups A polymerization stock solution having the composition shown in Table 7 is poured into a polytetrafluoroethylene tube with an inner diameter of 3 mm, a thickness of 71 m, and a length of 30 cm. The top of the seventh stage was assembled in a constant temperature water bath at a temperature of 70C, and the bundle of the second stage was carried out in an air heating furnace of /20C under the conditions shown in Table 1. y
Obtain d - (2) Evaluation of degree of swelling of cylindrical transparent electric composite Immerse the chassis body,
Polished glass... JK - Vertical directional force) using a cassette meter) to determine the outer diameter (ro), length 10) of the vehicle assembly before swelling and the outer diameter (r), length 1) of the chassis body after swelling. : Calculated from the following formula by measurement.

■oro2j0 ■Volume before performance ■: Volume after swelling (3) Evaluation of light focusing performance FIG. 1 is an explanatory diagram of a spot size measuring device showing light focusing performance. The original axis of the sample lens (1) is the light of the device! Ill (J) and adjust it so that it matches 1-1, and place the stage (
(not shown) on top. The output light of the He-Ne laser (3) is converted into parallel light with a diameter larger than the diameter of the sample lens by a beam extractor/inder (Q) VC. When this parallel light is applied to a sample lens having a length of 74 pinches, a spot image is generated on the other end surface. This image r microscope (S
), the spot image (9) is photographed by a television camera (1), and displayed on the screen of a television monitor (i) via a camera controller (7).

The camera controller has a function to display the entire light intensity distribution curve (/l) at the position of the cursor (/) on the screen of the TV monitor. Obtaining the curve allows you to determine the spot size.

Figure 1 shows the 'Itbk distribution curve of the photographic image.

The spot size is a distance d which is 1/2 of the maximum value.

Example 1 A cylindrical transparent bundle Kaf: ethylene glycol dimethyl ether (I, isopropyl ether) was prepared in a mixed solution heated to /i5C. When the degree of swelling was measured after soaking for 72 hours and 73 hours, the results were tdada, lφs, and t, respectively.
, qss was constant □14 The sample soaked for 1 hour was immediately treated with ethylene glycol dimethyl ether 5
Transfer into a 65C solution consisting of syH part, isobutetyryl ether qs7HH part, and 1 part by weight of heptafluorobutyric acid,
After soaking for 1 hour, it was then transferred to a 63C reaction solution consisting of ethylene glycol dimethyl ether SS, isopropyl ether qs, and heptafluorobutyric acid 2 parts by weight), and further soaked for 1 hour. Ethylene glycol dimethyl ether"'heavy'M
The 0-soaked fk sample was transferred to an A5C reaction solution consisting of IJ, isopropyl ether daS, and heptafluorobutyric acid, and immersed for 30 minutes.
After immersing in metal at room temperature for 1 hour and replacing the solvent, drying under reduced pressure at 70C for a μ hour, and then drying under reduced pressure at /θC for 1 hour, remove from the dryer and evaluate light focusing performance. did. The spot size d of this sample is stt
The cylindrical transparent polymer was composed of ethylene glycol dimethyl ether sobMs and isopropyl ether SO, and the cylindrical transparent polymer was 0! When the degree of swelling was measured by immersion in a mixed solution humidified by iC for 13 directions, 79 hours, and /S hours, Q i 'A 3, i'A3s, ilf
'A was almost constant at 015:16' Immediately immersed the sample in ethylene glycol dimethyl ether! Olj
Amount &lS-isopropyl ether! ; Changed name of ASC consisting of O Kyo Fubu, Heptafluoro Intoxication/Sato Nezumi, Liquid V
After straining at 7 o'clock, drink and add ethylene glycol dimethyl ether.
It was immersed for 7 hours in a reaction solution consisting of 1 part of inpropyl ether SO, 1 part of heptafluorobutyric acid, and 11 parts of ethylene glycol dimethyl ether SO,
Isopropyl ether! 0 parts by weight of 6SC and 1 part by weight of heptafluorobutyric acid. After immersion, the sample was taken out of the container and soaked in methanol at room temperature for 1 hour, after which the solvent was replaced, dried at 70C for several hours, and dried under reduced pressure for 2'1 hour in a coarse oven.・Take it out from the dryer and set the light year east performance to n'
□ Spot size d of this sample was 7 μm ○ Examples 3 to 9, Comparative Examples 1 to 3 Same as Example 1 except that the swelling conditions and reaction conditions were changed as shown by the second person. A Tsum-focusing synthetic resin body was prepared in the same manner, and Kyushu-ken FT12 was attached to the needle side. The results were also shown to a second person.

*The reaction was performed using OGDM that was sequentially immersed and treated in the order of ■■ [stock].
: Ethylene glycol dimethyl ether IPE :
Isopropyl ether MeOH: Meta/-IQtQAc: Ethyl acetate & FPA: Octafluoropentanoic acid H (CF, C
F, )2 Co, H FBA: Heptafluorobutyric acid C,F, Co, H /2FHA: Dodecafluorohebbutanoic acid H (CF,
CF, ), Co2H /, ? FOA: heptadecafluorooctanoic acid C7F
Ill C02H 3FE: Trifluoroethanol CF, CH, 0H 3FAA: ) Lifluoroacetic acid CF, Co2H

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of a spot size measuring device. FIG. 1 shows a light amount distribution curve of a spot image. /: Sample 3: Ke-Nθ laser beam; Beam expander s: FJA microscope A: Television camera: Camera controller g: Television monitor

Claims (1)

[Claims] After a cylindrical transparent polymer containing an epoxy group is immersed in a swelling liquid that satisfies formula (1) and swelled to a predetermined volume, the polymer has a reactivity with the epoxy group.・Sequentially immersion in two or more reaction solutions with different contents of low-molecular-weight compounds that react to produce a polymer having a refractive index lower than that of the bundle, from a solution with a low concentration of low-molecular-weight compounds to a solution with a high concentration of low-molecular-weight compounds. 1. A method for producing a light-focusing synthetic resin body, which comprises diffusing and reacting a low-molecular compound into a polymer, followed by drying. ■ l/≦−≦3. θ (1) O [In the formula, vo is the volume of the polymer before immersion in a swelling liquid\■ is the volume of the polymer immersed in the liquid and swollen until the liquid content in the polymer becomes almost constant. ]