JPS63227603A - Cured polymer having high refractive index and production thereof - Google Patents

Abstract

PURPOSE:To obtain a cured material suitable for optical uses, having high refractive index, high transparency and excellent surface hardness in polymerizing and curing a C=C unsaturated compound, by adding triphenylsilane and 1,1,8,8-tetraphenyldisiloxane to the polymerization system. CONSTITUTION:In polymerizing and curing one or more of C=C unsaturated compounds (e.g. styrene, methyl acrylate, ethylene glycol diacrylate and triallyl trimellitate), generally 25-75pts.wt. of triphenylsilane and/or 1,1,8,8- tetraphenyldisiloxane based on 100pts.wt. C=C unsaturated compound is added to the polymerization system and the unsaturated compound is polymerized in the presence of a radical polymerization initiator such as preferably benzoyl peroxide at room temperature-150 deg.C to give a cured material having high refractive index.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high refractive index polymerized cured product and a method for producing the same.
More specifically, the present invention relates to a high refractive index polymer cured product that can be used for optical applications and the like.

Since plastic is easy to mold and is easy to mold, it is also widely used for optical products such as Len-i-prisms. Highly transparent plastic materials conventionally used for optical applications include, for example, methyl methacrylate, diethylene tallycol, and allyl carbonate.
*, polycarbonate, polystyrene, etc. However, the first generation plastic materials have undesirable rAi porosity such as less than 10 years,
Methyl methacrylate-! ;Ethylene tallicol and suaryl carbonate resins have relatively low refractive indexes (about 1.49 to 1.50), so when this is taken as a ratio, the center thickness and edge thickness of the L lance are large. It has the problem of becoming.

In addition, polycarbonate, polystyrene, etc., exhibit a relatively high refractive index (about 1.58 to 1.59), but 1)
Because the surface hardness is extremely low (pencil hardness B or less), the surface is easily scratched, and it is difficult to perform precision machining such as cutting and polishing. It has drawbacks such as being easily oriented during the process of C= By coexisting a specific organosilicon compound when C-unsaturated compounds are polymerized, a polymerized cured product having a high refractive index can be produced without impairing its transparency and maintaining good surface hardness. The present invention has been completed and the present invention has been completed.
In the polymerized cured arm whose main component is
A high refractive index polymerized cured product that is specially sold as containing triphenylsilane and/or 1.1°8.8-detraphenyldicy0+san, and at least one C═C unsaturated compound is polymerized and cured. In this case, triphenylsilane and/or
1.1.8.High refractive semi-polymerized cured product gAh characterized by the coexistence of 8-tetraphenyldyl 0+san
In the present invention, the C═C unsaturated compound includes:
Any known C-C unsaturated monofunctional upper compound or C-C unsaturated polyfunctional compound can be used as long as it can be made into a liquid by dissolving it in a liquid or other liquid compound at room temperature. can also be used. As the C-C unsaturated monofunctional T-summer compound, any known vinyl polymerizable T-summer can be used, and specific examples thereof include 1 styrene 1 00 styrene 1
Vinyl compounds such as α-methylstyrene, methyl acrylate Schiff 0 + syl acrylate 1 acrylic acid esters such as benzyl acrylate - methyl methacrylate 1 syl methacrylate 1 phenyl methacrylate 1 benzyl methacrylate, etc. I can list many.

Examples of C═C unsaturated polyfunctional compounds include didinylben 1! vinyl compounds such as ethylene glycol diacrylate, 1 trimethyol diacrylate, 1 pentaerythritol triacrylate, 1 polyfunctional acrylate compounds such as tetramethyl methane tetraacrylate, 1 ethylenetalicol dimethacrylate) trimethyl 0- Polyfunctional methacrylate compounds such as bacitorimethacrylate 1 Diethylene glycol Salaryl carbonate S Diallyl phthalate 1 Diallyl isophthalate 1 Triallyl cyaslate Triallyl isocyanurate 1 Triallyl trimellitate or soluble polymers thereof, etc. Examples include furyl compounds. In the present invention, one type or two or more of the above C-C unsaturated compounds can be appropriately selected and used, but 1
In order to further increase the amount of refraction of the obtained polymerized and cured product, it is preferable that the polymerized and cured product of the single e)mer itself has a high refractive index. In order to obtain a polymerized cured product having a certain degree, it is preferable to use about 5 to 100% of a C═C unsaturated polyfunctional 7l7-compound to form a cross-linked ms-dimensional structure.

Triphenylsilane used in the present invention and 1.1°8.
8-Tetraphenyldyl 0+san is colorless, has good thermal stability, dissolves uniformly in the cured polymer of C═C unsaturated compound, and has the effect of increasing the refractive index by 1 in its molecular structure. Furthermore, the use of these compounds does not cause the yellowing that tends to occur in high refractive index semi-plastics, but rather has the effect of preventing yellowing.

This is because the St atoms in the molecule do not form double bonds and their conjugated systems that cause coloration, as is usually the case with bulky carbon atoms, and the 5 i and -B groups in the molecule This is thought to be due to the destruction of the coloring center. Triphenylsilane and 1.1.8.8-tetraphenyldisio! 'J: All J are known organosilicon compounds.

In producing the polymerized cured product of the present invention, known polymerization methods can be employed, such as thermal radical polymerization, photopolymerization, and the like.

According to the thermal radical polymerization method, the polymerized cured product of the present invention can be obtained, for example, as follows: ◇ That is, one or more C═C unsaturated compounds, triphenylsilane and/or a 1 .1.8.8-Tetraphenyldisimi 1 and 5! The cured product of the present invention is prepared by mixing and dissolving a cal polymerization initiator to obtain a homogeneous polymerization solution (which may be heated if necessary), and placing this polymerization solution in a polymerization container and heating it. Obtainable. Even if the above polymerization solution is left at room temperature for several days, the components do not precipitate and remain uniformly transparent. ◇As the radical polymerization initiator, known books can be used, such as penlyyl perio+cyto, 2 .4-
Jig 00 Penriil Beruo + Shito 1 G-I-Putyl Peruo + Shito, Shiitsubu 0ji Ruperuo Shiji Carbonate 1
Jiku! Examples include Ruberio Shito-7+ and the like, and one or more of these can be used. The heating temperature may be appropriately selected depending on the type of polymeric island initiator used, but it is usually from room temperature to about 150°C. However, in order to prevent residual strain from occurring due to the number of polymerizations, it is preferable to avoid rapid temperature increases at the initial stage of polymerization and to gradually increase the temperature to allow polymerization to proceed slowly. The polymerization time is also not particularly limited, but may be approximately 162 to 24 hours. At this time, any ordinary container can be used for the polymerization, but for example, a glass mold with a polished surface can be used. For example, a product with a desired shape can be obtained.

The amount of triphenylsilane and/or 1.1゜8.8-tetraphenyldisio+san to be added is approximately 20 to 120 kg per 100 kg of the C-C unsaturated compound, preferably 26 kg. It should be about 75 heavy ships. 25
When the amount is less than n1, the effect of increasing the refractive index of the obtained polymerized and cured product is poor. On the other hand, if it exceeds 75 parts by weight, it will be difficult to prepare a polymerization solution, and the hardness of the resulting polymerized cured product will decrease. The amount of radical polymerization initiator added is particularly
Although not limited, the amount may be usually about 1 to 8 parts by weight, preferably about 8 to 6 parts by weight, per 100 parts by weight of the C--C unsaturated compound. In addition, in the present invention, in the presence of a radical polymerization initiator, the addition reaction of a compound having H5i triple groups to a Kc=c double bond and the polymerization reaction of a C-C unsaturated compound occur in a competitive manner, so that triphenylsilane and/or t
There is a possibility that a part of ri 1.1.8.8-tetraphsynyldisiloxane is covalently bonded to the resin skeleton by the addition reaction. In view of the reliability, it is desirable to use a polyfunctional hexamer as the C--C unsaturated compound.

In addition, depending on the photopolymerization method, f of C,,=C unsaturated compound
ill or 2 or more, triphenyldine and/or a
1.1.8.8-Tetraphenyldyl 0+san and a photopolymerization initiator are dissolved and mixed to form a transparent polymerization liquid, and this is placed in a transparent polymerization container and irradiated with light to produce the polymerized cured product of the present invention. can be obtained. As a photopolymerization initiator, any known initiator used in photovinyl polymerization can be used, for example, phenylketones such as 1-siloxane + silphenylketone N-betinlJI/dimethyl ketal. etc. can be mentioned. Further, the C--C unsaturated compound to be used is not particularly limited, but particularly preferred examples include acrylic esters, methacrylic esters, and the like. The wavelength L1 of the irradiation light may be appropriately selected depending on the type of photopolymerization initiator used, but it is within the wavelength range of normal photocuring, that is, from ultraviolet to visible light (250 to 6501
1111) or so. The irradiation time may be selected appropriately depending on the wavelength and intensity of the light 1 polymer solution composition, etc., and is usually about several seconds to several hours ◇Triphenylsilane and /X
The amount of 4t, t, s, s-tetraphenyldyl 0+san to be added may be the same as in the case of radical polymerization. In addition, the amount of the photopolymerization initiator added is not limited to a certain level;
It may be selected as appropriate, but usually C-C unsaturated compound 100
The colorless and transparent polymerized cured product of the present invention thus obtained has triphenylsilane and/or 1.1.8 in the resin skeleton.
．． 8-Nato 5 Fusu 24650 people, 1
Even after a long period of time of more than a year, there is no change in quality such as yellowing, and the refractive index and Atsube number are 1.50 to 1.
They are about 62 and about 65-80. In addition, the organosilicon compounds contained in the polymerized cured product of the present invention are all high-boiling point compounds, and there is no problem in using them at room temperature. It can be used not only as an optical plastic material such as, but also for ordinary plastics, etc. 1, in particular, for imparting aesthetic appearance such as high refractive index, high transparency, and luster.

Effects of the Invention According to the present invention, the following effects are achieved.

(1) The polymerized cured product of the present invention is colorless and transparent, has a high refractive index, does not cause changes in quality such as yellowing over a long period of time, and has sufficient surface hardness. .

(2) When producing the polymerized cured product of the present invention, by appropriately selecting a polymerization container, a product with a desired shape can be obtained extremely easily, and by controlling the amount of each component added, the desired shape can be obtained. It can be a plastic material having a refractive index and a surface orthosis of .

Examples and comparative examples are given below to further clarify the present invention.

Examples 1 to 8 Triallyl cyanurate (TAC), liphenylsilane (rps), and penlylcyanurate (BPO) were mixed at the charging ratio (heavy part) shown in Table 1 and heated to about 40°C.
A transparent polymerization solution was prepared by heating to IIi. This polymerization solution was put into the part (4) of the polymerization container shown in Figure 1, which was composed of a mold (1), Paragyu: J (2) (soft gjyg riethyre: made by J), and a spring (3). , in air bath (open)
After heating at a bath temperature of 60°C for 5 hours, the bath temperature was gradually raised to 120°C over 10 hours, and held at 120°C for 1 hour. The temperature was lowered to .degree. C., and the cured product was taken out from the polymerization container to obtain a cured product of the present invention.

The physical properties (refractive index, Atsube's number, and pencil hardness) of the obtained polymerized cured product were measured. The results are sent to Daiichiki Kogyo Co., Ltd.
The 0 lead 11 hardness measured using a turbidity meter ND-H@7 type was measured according to JIS A-64oO (t97s). Furthermore, the temperature at which dehydration started in the thermogravimetry analysis of the polymerized cured products of Examples 1 to 8 was approximately 160° C. in all cases.

Comparative Example 1 A cured polymer was obtained in the same manner as in Example 1 except that triphenylsilane was not used. Its physical properties are shown in Table 1.

Table 1 TAC:) Reallyl cyaslate 7'PS:) Riphenylsilane BPO, penlylyl peroxide Example 4 Ethylene dilycol dimethacrylate (HDM), phenyl methacrylate (PM)% triphenylsilane (r
ps> and Shiitsubu 0 Go Rubelo Shiji Carboner)
(IPP) at room temperature, the preparation ratio shown in Table 2 (Fudobe)
to prepare a polymerization solution.

This polymerization solution was placed in a polymerization container shown in FIG. 1, and left standing in a constant temperature water bath at 40° C. for 16 hours. Next, the polymerization container was transferred to an air bath and held at 60°C for 1 hour, and then at 80°C for 1 hour, and then cooled to room temperature to obtain a colorless and transparent polymer sandwich of the present invention. Table 2 shows the physical properties of the obtained polymerized cured product.

Comparative Example 2 A cured polymer was obtained in the same manner as in Example 4, except that TPS was not used and IPP was used in half the amount. The physical properties are the second
Shown in the table.

Example 6 Trimethyolup-D vantriacrylate (TMPTA
) S phenyl methacrylate (PM) was mixed at the charging ratio shown in (G) (Jyusha Department) to prepare a polymerization solution. This polymerization solution was placed in a polymerization container shown in FIG. 1 and heated in the same manner as in Example 4 to obtain a polymerized product of the present invention. The physical properties are shown in Table 2. Comparative Example 8 A cured S polymer product was obtained in the same manner as in Example 5 except that TPS was not used and IPP was used as a half mold. The physical properties are the second
Shown in the table.

Table 2 El) M, ethylene dilycol dimethacrylate TMP
TA:) Rimethyolup0bantriacrylade PM
, phenyl methacrylate TPS: ) Riphenylsilane ipp: Shiitsubu 0jiruoheroshidicarbonate Example 6 triallyl cyanuride) (1'A(-') 1 o
1, 1.8.8-Detraphenyl dichloromethane (1°I)l) The white and convex portions of 2.5 m<h were mixed, and the mixture was humidified to about 40° C. to obtain a polymer solution. This Uraishin, the first
Place it in the polymerization container shown in 1.
C for 5 poems 1iJ, then /itnu was gradually increased to 120℃ over 6 poems, and the temperature was 411. The elephant was cooled down to 60°C over 4 hours to obtain a cured product. 71-): 1.600.Atsube>/: 88 *Pencil hardness: 2110 Total 117
TA) 6010111i et al., phenyl methacrylic) (PA7) 10011 (btfrp, triphenylsilane<l'Ps)B□masu-XiRi<and i-
Shido 0 Shishiku 0 to 10 syl phenyl ketone 0.8111
The iJ part was mixed in with the older brother, and 1.

This Iit gojo is carried out in the polymerization container shown in its 114 [However, 5;! Mold (1) is made of 1 tray made of Virex crow (27 is a rotating 4L tie at room temperature and elastic comb), and 25 (1'
Unexpected paddy loaded with ultra-high pressure water lamp 1<f split neck uzs-2
Light was emitted from each of the upper and lower crows for 8 minutes each using bxll (manufactured by Ushio Ki Co., Ltd.). In this way, the colorless and transparent Honbutton Ming Jiai Kyoukai Hatsu (J! Mesa 8.0) was 1;I. 7
'L: 1.68B, Atsbe number = 88. Rigidity: B#0 Comparative Example 4 A fJc composite compound 4 with a thickness of 8.0 In was made in the same manner as Examples 7 and 1 except that TPS was not used. n
:1.549. Atsube: 42. From the results of 4M0 or higher, the cured product of the present invention exhibits a high ItdIIt rate due to the presence of triphenylsilane or 1.1.8.8-tetraphenyl. Figure 15 shows that transparency and table IMi identity are maintained.
1 One Sheep Gun Φ1 17th (1s book 9Omin
-Q't-show- of the blood vessel used for Q't
It is 1+1+.

(17...Shi Building (2)...Barashin (:
B)...Spring (4)...Part where the stopper is inserted (and above)

Claims (2)

[Claims] (1) In a polymerized cured product containing at least one type of C═C unsaturated compound as a main component, the polymerized cured product contains triphenylsilane and/or 1,1,3,3-tetraphenyldisiloxane. High refractive index polymerized cured product. (2) When polymerizing and curing at least one C═C unsaturated compound, triphenylsilane and/or 1,1,3
, 3-tetraphenyldisiloxane.