JPH0391517A - High-refractive index transparent resin and its production - Google Patents

Abstract

PURPOSE:To obtain the title resin which is excellent in optical properties, mechanical properties, heat resistance, etc., and is useful as the material of plastic lenses by copolymerizing a diphenylethylene copolymer terminated with an active double bond with a monomer which can give a homopolymer of a high refractive index. CONSTITUTION:A high-refractive index transparent resin is produced by copolymerizing a polymer (A) which has a main chain comprising a diphenylethylene copolymer composed of repeating units of 1,1-diphenylethylene units and vinyl-aromatic compound units and/or conjugated diene units and having a number-average mol.wt. of 500-20000 and its terminated with an active double bond (wherein styrene is desirable as the vinyl-aromatic compound monomer which forms the above main chain structure, and 1,3-butadiene is desirable as the conjugated diene) with a monomer (B) which has a functional group reactive with the active double bond and can give a homopolymer of a refractive index >=1.5 (e.g. styrene, phenyl methacrylate or diallyl phthalate) in a weight ratio of A to B of 10/90-90/10.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a transparent resin having a high refractive index, and more specifically, to a diphenylethylene copolymer and a homopolymer having an active double bond at the molecular end. The present invention relates to a transparent resin made of a copolymer of a compound having a high refractive index with a monomer, and a method for producing the same.

Since the high refractive index transparent N4 resin of the present invention has excellent optical properties, mechanical properties, heat resistance, etc., it is expected to be used as a material for plastic lenses and prisms for glasses, optical machines, optoelectronics, etc. .

[Conventional technology]

In general, plastic optical materials are not comparable to inorganic glass materials in terms of the diversity and stability of optical functions, but they are lightweight, easy to mold, have excellent impact resistance, dyeability, and safety, and are also non-toxic. It has the advantage of being excellent in mass production of spherical lenses.

Plastics used as optical materials include transparent thermoplastic resins such as polymethacrylate, polystyrene, polycarbonate, and styrene-acrylonitrile copolymers, and thermosetting resins such as diethylene glycol bisallyl carbonate (general name: CR-39). is generally known.

In addition, as a new optical plastic material, a nuclear halogen-substituted aromatic compound polymer (Japanese Patent Application Laid-Open No. 55-069543
No. 57-002312, No. 57-028
1) Publication No. 7, Publication No. 58-166214, Publication No. 60-
137912, 60-124606, etc.), polymers with heavy metals introduced into the molecule (Japanese Unexamined Patent Application Publication No. 1983-1983),
No. 147101, No. 57-005705, No. 57-0281) No. 5, No. 5B-0281) No. 6, No. 59-161416, etc.), having a (meth)acryloyl group and a hydroxyl group in the molecule. A copolymer of a nuclear halogen-substituted aromatic compound and a polyfunctional isocyanate compound (see JP-A-60-051706) has been proposed.

[Problem that the invention seeks to solve]

The above-mentioned thermoplastic resins not only have low surface hardness and are easily scratched, but also have a low glass transition point, high hygroscopicity, and are prone to molecular orientation during molding, resulting in birefringence. It is only used for some purposes, such as sunglasses.

In addition, CR-39 has a high surface hardness and is excellent in transparency, heat resistance, dyeability, etc., so it is used in large quantities especially in mirror layer lenses because it has a refractive index of 1.49 to 1.50. is lower than 1.52 to 1.53 for crown glass,
When used as a concave lens, the end thickness becomes larger than that of a glass lens.

Therefore, the refractive index is at least 1.53, preferably 1.53 or more. '55 or above and other characteristics are CR-39
There is a demand for a high refractive index transparent resin that has properties equal to or better than that of .

The techniques cited in the above publication were proposed to meet these demands, but all of them involve compositions consisting of a low molecular weight compound having active double bonds in several M1) molecules and a radical polymerization initiator. Transparent resin is manufactured by injecting a material into a mold of a predetermined shape and curing it by heating. Generally, when heating and curing low molecular weight compounds with radical polymerizability such as styrene, methyl methacrylate, and the above-mentioned CR-39, large heat of polymerization is generated depending on the conditions, causing phenomena such as foaming, cracking, and sometimes carbonization. Furthermore, since these low molecular weight compounds inherently have a large curing shrinkage rate of around 10 to 20%, curing flaws ξ are likely to occur in the cured product. Therefore, in order to obtain a molded product with less curing loss ξ using these low-molecular compounds, the polymerization method involves raising the temperature stepwise from room temperature to high temperature over a long period of 20 to 30 hours to generate polymerization heat. It is necessary to adopt a method of suppressing this, making it difficult to mass-produce.

Furthermore, when using nuclear halogen-substituted aromatic compounds,
During heat curing, halogens are released and lenses tend to become colored, and when heavy metals are introduced, monomers containing heavy metals are generally difficult to dissolve in other monomers, and these copolymers have optical problems. For copolymers of nuclear halogen-substituted aromatic compounds and polyfunctional isocyanate compounds, which have low transparency, the curing method requires first a urethane reaction and then radical curing, which requires a complicated stepwise process. Not only does it require high temperatures and a significantly long curing time, but the mold release properties of the cured product are poor.

An object of the present invention is to provide a high refractive index transparent resin that has excellent optical properties, mechanical properties, and heat resistance, has a small curing shrinkage rate, and can be cured in a short time, and a method for producing the same.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have developed a diphenylethylene copolymer having an active double bond at the end of the molecule, and a monomer of a compound having a functional group copolymerizable with this copolymer. A high refractive index transparent resin that can be molded in a short period of time, has extremely low curing shrinkage, and has excellent optical properties, mechanical properties, heat resistance, and other properties due to the selection of monomers. The present invention was completed based on the discovery that the following can be obtained.

That is, the present invention consists of the following configuration.

(1) A: 1)-Diphenylethylene units and vinyl aromatic compound units and/or conjugated diene units are used as repeating units, and a diphenylethylene-based copolymer having a number average molecular weight of 500 to 20.000 is used as the main chain, Polymer B having an active double bond at the end of its molecule: A compound having a functional group that reacts with an active double bond, the homopolymer of which has a refractive index of 1.5 or more A monomer of the above A and B 10/90≦A/B≦90/10 (heavy i
A high refractive index transparent resin characterized by being made of a copolymer with a ratio of # reference).

(2) The high refractive index transparent resin according to claim 1, wherein the vinyl aromatic compound is styrene.

(3) The high refractive index transparent resin according to claim 1, wherein the conjugated diene is butadiene.

(4) In claim (1), B is an aromatic vinyl compound, an aromatic (meth)acrylate, a di(meth)acrylate, a hydroxy(meth)acrylate, an allyl diglycol carbonate, and a phthalate. A high refractive index transparent resin characterized by being at least one compound monomer selected from the group consisting of esters.

(5) A method for producing a high refractive index transparent resin, which comprises copolymerizing A and B according to claim (1) in the presence of a radical polymerization initiator and/or a photopolymerization initiator.

(6) In the method for producing a high refractive index transparent resin according to claim (4), a mixed solution consisting of A, B, a polymerization initiator, a resin component added as desired, and various additives is prepared by a casting method. A method for producing a high refractive index transparent resin, which comprises polymerizing A and B by thermosetting or photocuring.

In the present invention, the polymer A has repeating units in the main chain consisting of vinyl aromatic compound units and/or vinyl aromatic compound units represented by the following formula (1): Or from the conjugated diene unit IJ! The number average molecular weight is 500~
It is a polymer consisting of a diphenylethylene copolymer of 20,000% and has an active double bond at the end of the molecule via an ester bond, an ether bond, a urethane bond, etc.

As the vinyl aromatic compound monomer forming the main chain structure represented by -formation (2) above, styrene, 〇-methylstyrene, p-methylstyrene, p-tert-7'thylstyrene, 1,3-dimethyl Examples include styrene, α-methylstyrene, p-methoxystyrene, etc., and styrene is particularly preferably used.

In addition, the conjugated diene forming the conjugated diene unit is 1
) 3-butadiene, isoprene, 2,3-dimethyl-1
, 3-butadiene, 1,3-pentadiene, etc., and 1,3-butadiene is particularly preferably used.
In that case, the repeating units include l, 2-bond units,
1=4-any bonding unit may be used.

In the present invention, a known anionic polymerization method is employed for producing the diphenylethylene copolymer.

IS l-diphenylethylene is difficult to polymerize alone by anionic polymerization, but it is known that it forms alternating copolymers with vinyl aromatic compounds and conjugated dienes (
Polymer 1etters, 2+ 1) 21(
1964), J. Polymer Sei, 4
．． 2219 (1966), 'Copolymerization-2J, P1
05-P1) 4, ■ Baifukan (1976), etc.

The diphenylethylene-based copolymer of the present invention is produced in view of the above-mentioned prior art, and depending on the molar ratio of 1,1-diphenylethylene and the vinyl aromatic compound or conjugated diene used, At least a portion of the chain structure contains alternating copolymer portions thereof. That is, the number of moles of Ll-diphenylethylene used is (M
l), the number of moles of vinyl aromatic compound or conjugated diene [
M8], (Ml)'', (Mg), most of the main chain structure becomes an alternating copolymer; on the other hand, (
If Ml) < (Ms), a copolymer containing an alternating copolymer portion in a part of the main chain structure is produced.

Copolymerization is usually carried out under an inert gas atmosphere such as nitrogen or argon, using an alkali metal or organic alkali metal as a polymerization initiator, and at a polymerization temperature of -100 to 150°C in an appropriate solvent.
It is carried out under the following conditions.

Examples of alkali metals as polymerization initiators include lithium, sodium, potassium, etc., and examples of organic alkali metals include ethyllithium, n-butyllithium, 5ec-butyllithium, terL-butyllithium, ethyl sodium, butadienyl dilithium, and butadiene. Known alkylated products, allyl compounds, and aryls of the alkali metals such as sodium dianion, lithium biphenyl, lithium naphthalene, lithium triphenyl, lithium fluorene, sodium biphenyl, sodium naphthalene, sodium triphenyl, sodium fluorene, and α-methylstyrene sodium dianion. Chemicals, etc. are used.

As a reaction solvent, aliphatic hydrocarbons such as n-hexane and n-heptane, aliphatic hydrocarbons such as cyclohexane and cycloheptane, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, etc. A single solvent or a mixed solvent of two or more of these ethers may be used.

The polymer having an active double bond at the molecule end of A2 can be obtained by introducing an active double bond at the molecule end of the diphenylethylene copolymer.

Introduction of active double bonds to the molecular terminals of the diphenylethylene copolymer can be carried out by treating the diphenylethylene copolymer using the method described below.

(1) The reaction solution after the copolymerization reaction of 1.1-diphenylethylene and the vinyl aromatic compound and/or conjugated diene,
Method of treatment with a cyclic ether compound such as ethylene oxide or propylene oxide, and then treatment with (meth)acrylic acid chloride (2) After the copolymerization reaction of 1.1-diphenylethylene with a vinyl aromatic compound and/or a conjugated diene The reaction solution of
A method of treating with an N-type ether compound such as ethylene oxide or propylene oxide, followed by treatment with water, hydrochloric acid, methanol, etc. to introduce a hydroxyl group at the molecular end, and then reacting with (meth)acrylic acid chloride.

(3) A method in which a hydroxyl group is introduced at the end of the molecule by the same method as in item (2) above, and then half-esterified using an α,β-unsaturated carboxylic acid anhydride such as maleic anhydride.

(4) A method in which a hydroxyl group is introduced at the end of the molecule by the same method as in item (2) above, and then a (meth)acryloyl group or an allyl group is bonded via a urethane bond (Japanese Patent Publication No. 47-197-
(Refer to Publication No. 016195) (5)! , the reaction solution after the copolymerization reaction of 1-diphenylethylene and a vinyl aromatic compound and/or a conjugated diene is treated with carbon dioxide, and then water,
A method in which the molecular terminal is converted to a carboxyl group by treatment with hydrochloric acid, methanol, etc., and then reacted with an unsaturated epoxy compound such as glycidyl (meth)acrylate.

(6) The reaction solution after the copolymerization reaction of 1.1-diphenylethylene and the vinyl aromatic compound and/or conjugated diene,
A method in which an epoxy group is introduced at the end of the molecule by treatment with a halogenated cyclic ether compound such as epichlorohydrin, and then reacted with an unsaturated carboxylic acid such as (meth)acrylic acid.

On the other hand, B: a compound having a functional group that reacts with an active double bond and whose homopolymer has a refractive index of 1.5 or more. Monomers include aromatic vinyl compounds, aromatic (meth)acrylates, One or more of di(meth)acrylates, hydroxy(meth)acrylates, allyl diglycol carbonates, and phthalic acid esters.

Specifically, aromatic hinyl compounds N: styrene, vinyltoluene, methoxystyrene, chlorstyrene, bromustyrene, iodostyrene, dichlorostyrene, dibromostyrene,
Short styrene, trichlorostyrene, tribromustyrene, triiodostyrene, p-styryltrimethylsilane, p-styryltrimethoxysilane,! - Vinylnaphthalene, 2-vinylnaphthalene, vinyl-α-naphthylphenylsilane, vinyl benzoate, vinyl 4-chlorobenzoate, vinyl 4-bromobenzoate, etc., aromatic (meth)acrylate $ll: phenyl methacrylate, phenyl acrylate , chlorophenyl acrylate, dichlorophenyl methacrylate, bromphenyl acrylate, dibromphenyl methacrylate, pentabromphenyl methacrylate, methoxyphenylacrylate, benzyl methacrylate, chlorobenzyl acrylate, bromobenzyl methacrylate, dibromobenzyl methacrylate, tribromobenzyl methacrylate, pentabromobenzyl methacrylate , dicyclopentenyl (meth)acrylate, dicyclopentenyl (
meth)acrylate, α-naphthyl methacrylate, β
- Naphthyl methacrylate, α-naphthyl acrylate, etc., di(meth)acrylate 1: L4-dimethacryloxybenzene, 1,4-dimethacryloyloxybenzene, phthalate-di(2-methacryloxyphenyl)propane-2, 2-bis(4-methacryloxyphenyl)propane, 2.2-bis(4-methacryloxyphenyl)propane, 2.2-bis(4-methacryloxyethoxyphenyl)propane, 2-bis(4-methacryloxyethoxyphenyl)propane Hydroxy (meth)acrylates such as -3,5-dibromphenyl)propane-2,2-bis(4-methacryloxyethoxy-3,5-dichlorophenyl)propane! 1:2-(4-hydroxyethoxy-3,5-dibromphenyl)2-(
4-Acryloxyethoxy-3,5-dibromphenyl)propane, 2-(4-hydroxyethoxy-3,5-
dibromphenyl)-2(4-acryloxy-3,5-
dibromphenyl)propane, 2-(4-hydroxyethoxy,)3,5-dibromphenyl)-2-(4-methacryloxyethoxy-3,5-dibromphenyl)propane, etc., allyl diglycol carbonate Phthalate esters such as diethylene glycol bisallyl carbonate:
Diallyl phthalate, diallyl isophthalate, dimethacryl isophthalate, 3.4.5.6-diallyl titrachlorophthalate, 3.4.5.6-dimethacryl titrabromophthalate, 3.4.5.6- Examples include diallyl titrabromo terephthalate.

The high refractive index transparent resin of the present invention comprises the above A: polymer and the above B
: A/B ratio (weight basis) with compound monomer is 10/9
0≦A/B≦90-/10, preferably 20/80≦A
/B≦80/20.

This copolymer is produced by polymerizing the above A: polymer and the above B: compound monomer in the presence of a radical polymerization initiator and/or a photopolymerization initiator using a known polymerization method. easily obtained.

As a radical polymerization initiator, acyl peroxy F1)
1: Benzoyl peroxide, 2.4-dichlorobenzoyl peroxide, octatool peroxide, etc., dialkyl peroxide, di-L-butyl peroxide, 2.5
-dimethyl-(t-butylperoxy)hexyne-3,
Peroxy ester M: t
-Butyl perbenzoate, di-t-butyl perphthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, etc., ketone peroxide III + methyl ethyl ketone peroxide, cyclohexanone peroxide, etc., hydroperoxide cheeks Peroxyketals such as t-butyl hydroperoxide, cumene haloroba-oxide, α-phenylethyl hydroperoxide, cyclohexenyl hydroperoxide, etc.: 1゜l-bis(t-butylperoxy)
Hexane, 1, l-bis(1, butylperoxy)-3
, 3,5-trimethylolcyclohexane, peroxydicarbonate M, di-1-propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and the like. The amount of the radical polymerization initiator used is sufficient within the range of a catalyst amount in a general sense, and is usually 10% by weight or less based on the total amount of the above A: polymer and B: compound monomer.
Preferably it is 51i amount % or less. Further, if necessary, curing accelerators such as tertiary amines such as dimethylaniline, organometallic compounds such as cobalt naphthenate, tin octylate, and iron acetylacetone may be used in combination.

As a photopolymerization initiator, benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, 2.2-jethoxyacetophenone, 2.2
-Dimethoxyphenylacetophenone, 2-ethylanthraquinone, etc. are used.

In the production of the high refractive index transparent resin molded article of the present invention, usually,
Casting method is adopted. For example, a mixture of the copolymerized acids A and B and the radical polymerization initiator and/or photopolymerization initiator is injected into a transparent mold held by a gas get or spacer made of an elastomer, and heated or After being cured by irradiation with actinic rays, it can be released from the mold to produce a molded article.

Curing conditions vary depending on the type of polymerization initiator used and the shape of the molded product, but in the case of heat curing using a radical polymerization initiator as the polymerization initiator, the temperature is usually 40 to 130°C,
Curing time rJ1) 0 minutes to 20 minutes 20 hours In the case of photocuring using a photopolymerization initiator, use a low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, argon gas laser, sunlight, etc. as a light source, and adjust the intensity of the light source. The active light is irradiated for several seconds to several tens of hours depending on the condition. Further, a post-heating treatment may be added as necessary after irradiation with actinic rays.

During polymerization, additives such as a mold release agent, ultraviolet absorber, antioxidant, color inhibitor, antistatic agent, fluorescent dye, and various stabilizers are added to the mixture of the copolymer component and polymerization initiator. can be selected and used as needed.

In addition, reactive sI bodies and radically polymerizable resins other than those mentioned above may be added as constituent components of the copolymer to the mixture of the copolymer component and the polymerization initiator within a range that does not impair the refraction and transparency of the resin. be able to.

Reactive monomers that can be added include, for example, aliphatic (meth)acrylates: methyl methacrylate, cyclohexyl methacrylate, ethylene glycol methacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc., which have a hydroxyl group in the molecule (meth)
Acrylate cheeks: (meth)acrylates with an epoxy group in the molecule, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, nigericidyl methacrylate, methacrylic acid, acrylic acid, acriminitril, vinyl acetate, allyl alcohol , methyl α-trimethylsilylacrylate, etc., and radical copolymerizable resins such as 1,12-polybutadiene resin and its derivatives f;l:NrSSO-PB-8
-3000゜G-3000, TE-1000, T
E-2000, CM-1000, TEAI-100
Epoxy acrylates obtained by reacting a polyfunctional epoxy resin and (meth)acrylic acid, such as 0 (manufactured by Nippon Soda ■, trade name), etc., and epoxy acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate. Examples include urethane acrylates.

[For production]

As described above, the high refractive index transparent resin of the present invention includes A: a polymer whose main chain is a diphenylethylene copolymer having a number average molecular weight of 500 to 20,000 and has an active double bond at the molecular end; B: It is characterized by being composed of a copolymer obtained by copolymerizing a compound monomer in a specific ratio with a homopolymer having a functional group that reacts with an active double bond and having a refractive index of 1.5 or more.

The refractive index (n'') of the L 1-diphenylethylene monomer used in the present invention is 1.61, and the C
1.45 of R-39 monomer (1 as a homopolymer)
．． 50), 1.54 of styrene monomer (1.5
9), 1°56 of divinylbenzel monomer (1.6
1), 1.52 of diallyl phthalate monomer (same 1.
57), etc., is extremely high. Therefore, A of the present invention
The refractive index of a polymer with a nidiphenylethylene copolymer as its main chain and an active double bond at the molecular end is 1.5.
7 to 1.64, and by copolymerizing it with B: a compound monomer whose homopolymer has a refractive index of 1.50 or more, a high refractive index of 1.55 to 1.62 is obtained. A transparent resin is obtained.

In addition, because the diphenylethylene copolymer has an active double bond at the molecular end, it can be easily made three-dimensional by radical curing and/or photo curing, and has excellent mechanical properties such as high surface hardness, solvent resistance, and heat resistance. An insoluble and infusible cured product with excellent properties can be obtained.

The curing shrinkage rate during curing is extremely small at around 1%, so
When this polymer is copolymerized with other monomers, the curing strain is significantly reduced, which not only suppresses the occurrence of cranks during cast polymerization, but also enables short-time molding.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples.

However, the scope of the present invention is not limited in any way by the following examples.

In the following examples, "1 part" and "1%" are based on weight unless otherwise specified.

(IIA nidiphenylethylene copolymer as the main chain,
Synthesis of polymers with active double bonds at the end of the molecule.

(a) Sample A-1 At -30°C in a nitrogen atmosphere, 0.1% sodium was added to tetrahydrofuran (hereinafter referred to as rTHFJ).
Sodium dispersion containing 9 mol (hereinafter referred to as rSDJ)
1) 1-diphenylethylene (
After adding 1 mol of styrene (hereinafter referred to as rDPEJ) and holding for 10 minutes, 1.1 mol of styrene C (hereinafter referred to as rstJ) was added to
The copolymerization reaction was completed by adding the mixture over a period of time and holding the mixture for an additional 3 hours. A portion of this polymerization reaction solution was taken out of the system, poured into a large amount of methanol, filtered, and dried under reduced pressure to obtain a white powdery polymer with a number average molecular weight of 3,000 (
It is a monodisperse polymer with a polydispersity of 1.12 (MW/Mn by GPC), and a molar ratio of DPE and St determined by pyrolysis gas chromatography (rpy-cc). Since the ratios were almost equal, it was confirmed that this polymer was a DPE-3L alternating copolymer.

The remaining polymerization reaction solution was treated with carbon dioxide and then hydrolyzed to give a number average molecular weight of 313. I 00, acid value 32.6
A diphenylethylene-styrene copolymer having a carboxyl group at the molecular terminal: Sample a-1 was obtained.

A 50% solution was prepared by dissolving 1.8 mol of the obtained sample a-1), 1.8 mol of glycidyl methacrylate, and 0.1 mol of benzyldimethylamine (nistylation catalyst) in toluene, and heated and held at 100 ° C. for 5 hours. After carrying out the reaction,
The reaction solution was poured into a large amount of methanol, and the precipitated solid content was filtered and dried under reduced pressure to obtain a polymer having a diphenylethylene-styrene copolymer as the main chain and an active double bond at the molecular end: Sample A- I got 1.

The obtained sample A-1 was a white powdery polymer having a number average molecular weight of 3,350° and a softening point of 185°C.

(B) Sample A-2 In a nitrogen atmosphere at -30°C, D
After adding 1 mol of PE and holding for 10 minutes, add 40% THF containing 1.1 mol of 1.3-butadiene (hereinafter referred to as rBD).
The solution was added over 3 hours and maintained for an additional 3 hours to complete the copolymerization reaction.

A part of this polymerization reaction solution was taken out of the system, poured into a large amount of methanol, filtered, and dried under reduced pressure to obtain a white powdery polymer with a number average molecular weight of 4°630 and a polydispersity of 1.
．． It was confirmed that this polymer was a DPE-Bd alternating copolymer because the molar ratio of DPE and BD determined by py-cc was almost equal.

The remaining polymerization reaction solution was treated with ethylene oxide, then methacrylic acid chloride was added and reacted, and then the reaction solution was poured into a large amount of methanol, and the precipitated solid content was filtered.
By drying under reduced pressure, a polymer sample A-2 having a diphenylethylene-butadiene copolymer as the main chain and having an active double bond at the molecular end was obtained.

The obtained sample, A-2, was a white powdery polymer with a number average molecular weight of 14.800 and a softening point of 128°C.

(C) Sample A-3 Under a nitrogen atmosphere at -30°C, a 40% THF solution containing 801 mol of sodium was added over 2 hours to a slurry in which SD containing 0.1 mol of sodium was suspended in THF. It was held for an additional hour. Next, 81 mol of DP was added and held for 10 minutes, then 1 mol of Stl was added over 3 hours, and the mixture was held for an additional 3 hours to complete the copolymerization reaction.

A part of this polymerization reaction solution was taken out of the system, poured into a large amount of methanol, filtered, and dried under reduced pressure to obtain a white powdery polymer with a number average molecular weight of 12°980 and a polydispersity of 1.
．． 23, and since the molar ratio of BD, DPE, and SL determined by Py-GC is almost equal, this polymer is a BD-DPE containing alternating DPE-St copolymer moieties in the main chain. It was confirmed that it was a -St terpolymer.

The remaining polymerization reaction solution was treated with ethylene oxide and then hydrolyzed to give a number average molecular weight of 413.05 G and a hydroxyl value of 29.
．． Sample a-3 was obtained: a butadiene-diphenylethylene-styrene terpolymer having a hydroxyl group at the molecular end of No. 4.

31 moles of sample a-obtained and 1.6 moles of maleic anhydride were dissolved in toluene to prepare a 50% solution #J4.
After carrying out the reaction by heating and holding at ℃ for 3 hours, the reaction solution was poured into a large amount of methanol, and the precipitated solid content was filtered and dried under reduced pressure to convert the butadiene-diphenylethylene-styrene copolymer into a main chain. A polymer having an active double bond at the end of the molecule: Sample A-3 was obtained.

The obtained sample A-3 was a white powdery polymer with a number average molecular weight of 3.200 and a softening point of 1) 0°C.

(ψ Sample A-4 At -30°C under nitrogen atmosphere, n - Bu Li
After adding 1 mole of DPEI to a THF solution containing 12 moles of O and holding for 10 minutes, 1.3 moles of styrene was added over 3 hours, and then 3)? rJI was retained. Then, 0.5 mol of α-methylstyrene (hereinafter referred to as α-MS) was added over 2 hours, and the mixture was maintained for an additional 1 hour to complete the copolymerization reaction.

A part of this polymerization reaction solution was taken out of the system, poured into a large amount of methanol, filtered, and dried under reduced pressure to obtain a white powdery polymer with a number average molecular weight of 12°120 and a polydispersity of 1.
, 25, and since the molar ratio of DPE, St, and α-MS determined by py-cc is almost always a part of the charged molar ratio, this polymer has DPE-3L-αMS containing DPE-5t alternating copolymer
6I confirmed that it was a terpolymer.

The remaining polymerization reaction solution is treated with epichlorohydrin and then hydrolyzed to form a number average molecule i2. Sample a-4 was obtained: a diphenylethylene-styrene-α/methylstyrene terpolymer having an epoxy group at the molecular end of I 50 and epoxy 1 to 2.260.

A 50% solution was prepared by dissolving 41 mol of the obtained sample a-4, 0.9 mol of acrylic acid, and 0.1 mol of benzyldimethylamine in toluene, and the reaction was carried out by heating and holding at 90'C for 3 hours. After that, the reaction solution was poured into a large amount of methanol, and the precipitated solid content was filtered and dried under reduced pressure to form a main chain of diphenylethylene-styrene-α-methylstyrene copolymer and an active double bond at the end of the molecule. A polymer having: Sample A-4 was obtained.

The obtained sample A-4 was a white powdery polymer having a number average molecular weight of 2.300 and a softening point of 170°C.

(2) High refractive index transparent resin - (f) (a) Examples 1 to 7 The A-diphenylethylene copolymer synthesized in the above item (1) was used as the main chain, and an active double bond was added at the molecular end. Polymer having: each of tA materials A-1 to A-3, B: various compound monomers having a functional group that reacts with an active double bond (the first
(see Table 1) and a specified amount (see Table 1) of a radical polymerization initiator (see Table 1), and if necessary, add a specified amount of various radically polymerizable monomers (see Table 1). In addition, a mixed solution was prepared.

This mixed solution was poured into a mold consisting of a glass plate with a diameter of 73 m and a gasket made of ethylene-vinyl acetate copolymer, and after being kept in a hot air circulation dryer adjusted to 80°C for 1 hour, the temperature was lowered to 1°C. ) The temperature was raised to 0° C. and further maintained for 1 hour for thermosetting, and then released from the mold to obtain the desired molded body of a high refractive index transparent resin.

The formulation of each resin component is shown in Table 1.

(b) Comparative Examples 1 to 6 Various radically polymerizable monomers, a mixture of sample A-1 prepared in the above item (+) (a) and a radically polymerizable monomer,
Sample a-1 prepared in the above section (+) (a), a mixture of (diphenylethylene-styrene copolymer) and a radically polymerizable monomer, the sample prepared in the above section (+) (d) F
1a-4 (diphenylethylene-styrene-α-methylstyrene terpolymer) and B: mixture of compound monomer having a functional group that reacts with an active double bond (see Table 1)
A mixed solution containing a radical polymerization initiator was prepared and poured into the same mold as above. Polymerization was started at 50°C, and after 18 hours, the temperature was gradually raised to 80°C, and the temperature was further maintained at 80°C for 2 hours for curing polymerization. After releasing the cured product from the mold, 2
Post-curing was performed by holding for a period of time to obtain a molded article.

In addition, when these mixed solutions were used and cured under the same curing conditions as in the above-mentioned Examples, except for Comparative Example 4, foaming and cracking were significant, and no molded bodies with measurable properties were obtained.

The formulation of each resin component is shown in Table 1.

(C) Characteristic evaluation test The following characteristic evaluation test was conducted on the molded article prepared in the above item (2).

The test results are shown in Table 1.

(2) Refractive index (ne) and Atsube number (Ab) Using an Atsube refractometer and using α-bromonaphthalene as a contact liquid, the refractive index (n) at 25°C was determined.

and Atsube number (A,) were measured.

(2) Light transmittance (T,) The light transmittance (T,) of a 2 m thick test piece was measured using a haze meter.

■ Curing shrinkage rate (V) The specific gravity of the casting liquid and the cured product was measured, and calculated using the following formula.

) ■Surface hardness (H2) Pencil hardness (H2) was measured according to JIS K-5400.

■ Glass transfer point (T,) From the measurement results of dynamic viscoelasticity, the glass transition point (T.

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(2) Water absorption rate (W,) The weight of the test piece before and after the immersion test in which the test piece was immersed in boiling water for 2 hours was measured, and the water absorption rate (Wl) was calculated.

■ Solvent resistance (S,) A rubbing test was performed on the surface of the cured molded product using absorbent cotton impregnated with methyl ethyl ketone, changes in the surface condition were observed, and the results were determined as solvent resistance (S,).

In Table 1: No OIR × Changes such as softening, dissolution, and decreased transparency is recognized.

■ Cutting workability (C1) Cutting was performed using a grinder, the cut surface, etc. were observed, and the cutting workability (C1) was determined.

Table 1: 0: Cleanly cut.

× Cracks, cutting powder residue, etc. are observed. I can't stand it.

As shown in Table 1, the high refractive index (transparent) resin of the present invention not only exhibits a high refractive index and high transmittance, but also can be cured under simple curing conditions and has an extremely low curing shrinkage rate. . It also has excellent properties such as surface hardness, glass transition point, water absorption, solvent resistance, and machinability.

On the other hand, in the comparative example, it is necessary to cure under complicated curing conditions, and a cured molded article with all these properties balanced has not been obtained.

(4) High refractive index transparent resin - [■] The main chain is the A-diphenylethylene-styrene-α-methylstyrene tricopolymer synthesized in item (1) (a) above, and has an active double bond at the molecular end. Polymer having (Sample A-
4) 60 parts, B: 30 parts of pendyl methacrylate monomer and 10 parts of trimethylolpropane trimethacrylate
2 parts of benzophenone (photopolymerization initiator) and 1 part of lauroyl peroxide were thoroughly mixed to prepare a mixed solution.

This mixed solution was injected into the same mold used in item (2) above, irradiated with active light for 20 minutes from a distance of 10 cm using a high-pressure mercury lamp, and then kept at 100°C for 1 hour. It was cured and released from the mold to obtain a molded article.

The obtained molded body has a visible light transmittance (T, ) of 90%,
Refractive index (n,) 1.60, Atsbe number (Ah > 32,
Curing shrinkage rate (V,) 3.8% Glass transition point (7°150
It was a tough, high refractive index transparent resin.

〔Effect of the invention〕

As shown in the examples above, the high refractive index transparent resin of the present invention has excellent optical properties such as light transmittance and refractive index, and also has high glass transition point and surface hardness, water absorption, solvent resistance, and processing properties. It is a molded product with excellent properties.

Therefore, the high refractive index transparent resin of the present invention and its manufacturing method are useful for lenses for 1lff mirrors, still cameras, video cameras, telescopes, solar concentrators, etc., prisms,
It can be used as a material for a molded body and a method for producing molded bodies that require the ability to transmit, reflect, and refract light, such as light guide elements such as optical waveguides, disks such as video disks, audio disks, etc.

) The present invention provides a high refractive index transparent resin useful as lenses and optoelectronic materials and a method for producing the same, and has extremely great industrial significance.

TECHNICAL FIELD The present invention relates to a high refractive index transparent resin and a method for producing the same, which is used for research and development of functional polymers.

A copolymer of a polymer whose main chain is a low molecular weight diphenylethylene copolymer obtained by anionic living polymerization and has an active double bond at the molecular end, and a compound monomer whose homopolymer has a high refractive index. However, it not only has an extremely high refractive index and visible light transmittance, but also has an extremely low curing shrinkage rate when producing molded products, and has other properties that are comparable to conventional lens resins. I discovered something.

Claims (6)

[Claims] (1) A: 1,1-diphenylethylene units and vinyl aromatic compound units and/or conjugated diene units are used as repeating units, and the main chain is a diphenylethylene copolymer with a number average molecular weight of 500 to 20,000. , Polymer B having an active double bond at the end of its molecule: A compound having a functional group that reacts with an active double bond, whose homopolymer has a refractive index of 1.5.
A high refractive index transparent resin comprising a copolymer of the above compound monomers A and B in a ratio of 10/90≦A/B≦90/10 (based on weight). (2) The high refractive index transparent resin according to claim 1, wherein the vinyl aromatic compound is styrene. (3) The high refractive index transparent resin according to claim 1, wherein the conjugated diene is butadiene. (4) In claim (1), B is an aromatic vinyl compound, an aromatic (meth)acrylate, a di(meth)acrylate, a hydroxy(meth)acrylate, an allyl diglycol carbonate, and a phthalate. A high refractive index transparent resin characterized by comprising at least one compound monomer selected from the group consisting of esters. (5) A method for producing a high refractive index transparent resin, which comprises copolymerizing A and B according to claim (1) in the presence of a radical polymerization initiator and/or a photopolymerization initiator. (6) In the method for producing a high refractive index transparent resin according to claim (4), a mixed solution consisting of A, B, a polymerization initiator, a resin component added as desired, and various additives is prepared by a casting method. A method for producing a high refractive index transparent resin, which comprises polymerizing A and B by thermosetting or photocuring.