JPS601213A - High-refractive index resin composition - Google Patents

Abstract

PURPOSE:A high-refractive index resin composition of excellent rapid cycle moldability, containing a (meth)acrylate monomer having a specified naphthyl skeleton and a saturated aliphatic hydrocarbon-type poly(meth)acrylate having a specified refractive index. CONSTITUTION:A polymerizable mixture consisting of (A) 30-95wt% polymer of formula I (wherein R<1> is H or CH3, R<2> is -CH2CH2O-, a group of formula II, etc., X is H, Cl, Br, CH3, etc., m is 1-3, and m=1 when R<2> is a group of formula II) or a mixture thereof, (B) 0-70wt% polymerizable monomer of formula III(wherein R<3> is H or CH3, R<4> is -CH2CH2)O-, a group of formula II, etc., Ar is a dihydric phenol residue, n is 1-3, and p is 0-4) or a mixture thereof, and (C) 5-30wt% polymerizable monomer having a refractive index >=1.45, represented by formula IV (wherein R<5> is H or CH3, R<6> is a q-valent saturated aliphatic hydrocarbon group, and q is 2-6) or a mixture thereof, where the total of (A), (B) and (C) is 100%.

Description

[Detailed description of the invention] Technical field of invention.

The present invention relates to a composition for a high refractive index resin having a refractive index of 1.58 or more, and particularly to a composition for a high refractive index resin having excellent high-speed moldability.

Conventional technology Inorganic glass has traditionally been used in many applications due to its excellent transparency, hardness, scratch resistance, weather resistance, etc. However, on the other hand, it has the drawbacks of being brittle, easily broken, and heavy. have. On the other hand, organic glass has advantages that inorganic glass does not have, such as lightness, safety, processability, and dyeability.
Polymers such as polymethyl methacrylate, polycarbonate, and diethylene glycol diallyl carbonate are currently used. For applications such as eyeglass lenses, there are extremely high expectations for organic glass due to its lightness and safety (resistance to breakage).

However, the diethylene glycol diallyl carnate polymer has a low refractive index (refractive index of 1.499) and has the disadvantage that it has to be thicker than an inorganic glass lens.

・In order to improve this drawback, attempts have been made to use a resin with a high refractive index, but I-restyrene (refractive index 1.5
9) Polycarbonate (refractive index 1.59) etc. are thermoplastic resins and have the disadvantage of poor solvent resistance, and because they are mainly molded by injection molding, they tend to leave distortions during molding. . From this point of view, several prior art techniques have been disclosed in which cross-linking polymerizable monomers with a high refractive index are used for heat curing. For example, JP-A-55-137
No. 47, No. 56-61411, No. 56-61412, No. 57-2311, No. 57-23124, No. 57
-23611, 57-28115, 57-28
No. 126, No. 57-28117, No. 57-28118
I can praise each publication in the issue.

However, in all of these prior art techniques, a desired cured product is obtained by injecting a homogeneous mixture of a monomer composition and a polymerization initiator into a casting jig and then carrying out thermal polymerization over a long period of time. However, because of this, the rotation of the injection molding jig for Note 7 is slow, requiring a large number of casting jigs, and the thermal energy required for polymerization, which takes a long time, is extremely low, resulting in extremely low productivity. It has the following disadvantages.

Purpose of the Invention In view of the shortcomings of the prior art, the present inventors conducted intensive research to develop a high refractive index resin composition with excellent high-speed moldability. )
The refractive index of the (meth)acrylate monomer and monomer derived from the acrylate monomer and dihydric phenol is 1.
By copolymerizing and curing a polymerizable composition consisting of a saturated aliphatic hydrocarbon-based polyfunctional (meth)acrylate that may contain 450 or more ethers, esters, and alcohols, a high refractive index can be obtained in an extremely short time. The present invention has been achieved by discovering that a high refractive index resin can be obtained which has the following characteristics and has excellent surface hardness, solvent resistance, heat resistance, impact resistance, dyeability, etc.

Therefore, an object of the present invention is to provide a composition capable of producing a high refractive index resin having a refractive index of 1.58 or more.

Another object of the present invention is to provide a composition capable of producing a high refractive index resin for lenses having transparency and colorless properties desirable for optical lenses.

Furthermore, other objects of the present invention are to provide excellent surface hardness, solvent resistance,
The object of the present invention is to provide a composition capable of producing a high cover refractive index resin gold for lenses that has heat resistance, dyeability, and processability.

Formation of the Invention The i#I refractive index resin composition of the present invention has the general formula (I) (
In the formula, R represents H or CH5'e, R2U -CT(
,,C) L20-.

X is H, C1r Br+ cH,, CI(,ol C6
represents H5 or C6H5O, m represents an integer of 1 to 3, R2 represents a polymerizable monomer or a mixture thereof 30 to
95% by weight, (B) general formula (II) (It) (wherein R3 represents H or CH3, R is -CH2C
H20-.

Ar represents all residues of dihydric phenol, n represents an integer of 1 to 3, and p represents an integer of O to 4) or a mixture thereof 0 to 70% by weight %
(Q) General formula (Ill) having a refractive index of 1.450 or more (wherein R5 represents H or CH, and R6 is a saturated aliphatic group which may contain an ether, ester, or alcohol with a valence of q) (represents a hydrocarbon group, q represents an integer of 2 to 6) or a mixture thereof 5 to 3
0% by weight, consisting of components (A), (B) and (C)
The amount of chorus is 100%.

Detailed explanation of the constitution of the invention In order to achieve the object of the present invention, the compound (A) of general formula (I) used in the method of the present invention must be
The amount of monomer used is 95N, preferably 33 to 9 (1% by weight, more preferably 35 to 855 to 85% by weight). Examples of such monomers include.

In order to achieve the object of the present invention, the monomer (B) of the general formula (It) used in the present invention should be 0 to 70'
ji amount, preferably 0 to 67% by weight, more preferably 0 to 65% by weight (note that 0% by weight includes the case where sweat body (B) is not present). By containing the monomer (B), peeling from the mold due to curing shrinkage r+- is minimized, and toughness or, in some cases, dyeability is improved.

Examples of such monomers include -OCH2CD20CO-CH=CH2 (R=H or C
H3) etc.

In the present invention, in order to achieve the object of the present invention, the monomer (C) of the general formula (g) should be contained in an amount of 5 to 30% by weight, preferably 10 to 27% by weight, more preferably 15 to 25% by weight. used in an amount of %. The use of monomer C) is suitable for the purpose of increasing the Atsube number, increasing the crosslinking density, and improving the solvent resistance, hardness, etc. of the copolymerized fracture product.

Examples of such monomers (C1 include: CH2=CH-C00CH2CH20COCH=CH2
CH2=CH-COOCH2CH20CO-CH=CH
2\/C CH2=CH-COOCH2CH20CH2CH2- etc. can be opened.

These monomers used in the present invention (however, monomers (
The total weight of A), (B) and (C) is 100 canes)
The mixing ratio of monomers (A
) If the proportion exceeds 95% by weight, the surface hardness, heat resistance, solvent resistance, and cutting workability of the cured copolymer will be insufficient, and conversely, if the proportion is less than 30% by weight, the surface hardness of the cured copolymer will deteriorate. Although solvent resistance can be improved, impact resistance and processability are lowered, which is not preferable.

In addition, the usage ratio of monomer (C) varies depending on the stacking of monomers (A) and (B), the amount used, the refractive index of monomer (C) itself, the number of functional groups, etc. I can't decide, but
At most 30% by weight.

If it exceeds 30% by weight, the surface hardness and solvent resistance of the cured copolymer, as well as the Atsushi number, will increase, but the refractive index, impact resistance, and processability will decrease, making it undesirable. It is undesirable because it is not easy to peel off from the mold and the surface precision of the cured product is deteriorated.

To produce a high refractive index resin from the composition according to the present invention,
It can be carried out by radical polymerization using a radical polymerization initiator. As the polymerization method, not only thermal polymerization but also a polymerization method using active energy rays such as ultraviolet rays and γ rays can be used, and by either method, a high refractive index resin free of optical distortion can be obtained in a short time.

In particular, polymerization using ultraviolet rays has the advantage that copolymerization can be carried out in a short time (Lj), and not only can production be significantly increased, but also a cured product with little optical distortion can be obtained, and is particularly suitable in the present invention. .

When carrying out thermal polymerization, common radical polymerization initiators such as benzoyl peroxide, diisopropyl peroxydicardenate, and azobisisobutyronitrile can be used.

In the case of ultraviolet curing, commonly known luhensoyl, penzoin methyl ether, penzoin ethyl ether, penzoin isoglobyl ether, benzoin isobutyl ether, 2-hydroxy-2-penzoylpronoyanine, and asobisuirin are used. Photosensitizers such as sobutyronitrile, benzyl, thioxanthone, etc. can be used. These radical polymerization initiators or photosensitizers are used in an amount of about 5% by weight at most based on the copolymer composition. Furthermore, when using radiation such as gamma rays, it is generally not necessary to add a polymerization initiator.

In addition to the above monomers, the copolymer composition according to the present invention includes an anti-yellowing agent (for example, triphenylphosphine, etc.),
A leveling agent (such as a fluorine surfactant) and an ultraviolet absorber (such as 2-(2-1 nitroxy-5-methylphenyl)-2H-benzotriazole) may be added within a range that does not interfere with polymerization and curing.

Furthermore, the lens according to the present invention can be produced by injecting the copolymer composition into a lens mold prepared with a glass mold and a gasket, and curing it by heating, irradiating with ultraviolet rays, or irradiating with other active energy rays. This is done by removing the mold afterwards.

Furthermore, the refractive index of the resin produced from the composition of the present invention is
The actual blade size depends on the blending ratio of raw materials, but it is 1°58 to 1.65.
General transparent thermosetting resin (urea resin 1.54
, melamine resin 1.55, alkyd resin 1.55, diallyl phthalate resin 1.56, diethylene glycol bisallyl carbonate resin 1.499), it is not bulky and has excellent heat resistance, surface hardness, etc. In addition to eyeglass lenses, the scope of use can be expanded to include camera lenses, light emitting diode encapsulants, lens adhesives, luminous bead binders, other optical elements, decorative castings such as buttons, paints, etc. It has great industrial significance.

EXAMPLES Hereinafter, the present invention will be explained in more detail by examples.
It goes without saying that the scope of the present invention is not limited to these Examples.

The physical properties of the molded products obtained in Examples and Comparative Examples were measured using the following test methods.

(1) Refractive index The refractive index at 20° C. was measured using an Atsube refractometer. Bromonaphthalin was used as the contact liquid.

(2) Hardness It was measured using a Percoll hardness meter.

(3) Surface condition: Visually observe the surface condition of the front and back sides of the molded product. ○ indicates that both the front and back sides are smooth, Δ indicates slight roughness on the surface, and Δ indicates roughness on the entire surface. It was set as ×.

(4) Light transmittance: 550 nm for a flat plate of copolymerized cured product with a thickness of 2WI+
The light transmittance at

(5) #4 impact test Based on FDA standards, the center of a flat plate of copolymer cured material with a thickness of 2 mm is 127 mm in height, 15.9 mm in diameter, and 16 mm in weight.
．． A 2g copper ball was dropped, and those that did not break were considered good.

(6) Heat Resistance Edges left in a hot air dryer at 120° C. for 3 hours were visually observed with no coloration or surface distortion as 01, and surfaces with surface distortion observed as ×.

(7) Dyeability The molded product was immersed in a 0.2% Disperse Brown 3 aqueous solution, immersed at 92° C. for 10 minutes, pulled out, thoroughly washed with water, and dried. Among these dyed molded products, those in which no dyeing unevenness was observed were rated O, and those in which some dyeing unevenness was observed were rated △.

Example 1 80 parts by weight of α-naphthogythacrylate, 20 parts by weight of dipentaerythritol hexaacrylate) 1ffL2--'
? 0.1 part by weight of 2-hydroxyprono-4,
Triphenylphosphine 0.1 part by weight as an anti-yellowing agent and 2-(2-hydroxy-5-methylphenyl)-2H-penzo) IJ azole 0.0 as an ultraviolet absorber
3 parts by weight were mixed to form a homogeneous composition. This was poured into a mold for a glass lens, and after degassing, it was heated to 20 cm using a 3 kW high-pressure mercury lamp with a lamp input of 80 W/(7).
Each surface was irradiated with ultraviolet light for a total of 20 seconds at a distance of .

Thereafter, the mold was removed and heat treated in an oven at 100°C for 1 hour to obtain a colorless and transparent lens with no optical distortion.

Table 1 shows the physical properties of the lens thus obtained.

Examples 2 to 6 Lenses were produced under the same conditions as in Example 1 by uniformly mixing various monomers with the monomer composition shown in Table 1.

Table 1 shows the measurement results of the lens physical properties of the polymer.

- Comparative Example 1 The monomer used in Example 1 was replaced with C!, which is commonly used as a monomer for producing waste! Ultraviolet rays were irradiated under exactly the same conditions as in Example 1 except that R-39 (diethylene glycol bisallyl carbonate) was used, but even after 10 minutes of irradiation, only a soft lump was obtained and the cured product could be used for lenses. Comparative Examples 2 and 3 Various monomers were uniformly mixed with a monomer composition outside the scope of the claims of the present invention, and l/lens were prepared under the same conditions as in Example 1. Table 1 shows the measurement results of the lens physical properties of the polymer.

From the above examples and comparative examples, the resin obtained using the polymerizable composition of the present invention is extremely suitable as a high refractive index resin, and is excellent when used in various heel applications. That should be obvious.

Example 7 50 parts by weight of α-naphthoxyethyl acrylate, 1 mole of an epoxy resin with an epoxy equivalent of 190 obtained by condensation of bisphenol A and epichlorohydrin, and 2 moles of acrylic acid were heated at 120°C in the presence of a lithium chloride catalyst. 40 parts by weight of epoxy acrylate obtained by heating reaction, 10 parts by weight of dipentaerythritol hexaacrylate, 2-pensoyl-2-hydroxypropane o, i
Part I, tris-(n-octyl) as an anti-yellowing agent
phosphite) was mixed and stirred well to uniformly dissolve the mixture. This was injected into a glass mold for sealing a light emitting diode, and the GaP diode element connected to the substrate via lead wires was immersed and degassed, and then exposed to ultraviolet rays from the surrounding area using a 3kW high-pressure mercury lamp with a lamp input of 80W/cIn. . It completely cured in 10 seconds and became a transparent sealed cured product with a refractive index of 1.596. Procedural amendment (voluntary) June 2, 1980, Mr. Manabu Shiga, Commissioner of the Japanese Patent Office, 1, Indication of the incident 1981 Patent Application No. 107952 2, Title of invention: Composition for high refractive index resin 3, Relationship with the amended person case Name of patent applicant (200) Showa Denko Co., Ltd. 4, Agent (3 others) 5. Column 6 of "Detailed Description of the Invention" of the specification to be amended, contents of the amendment (a) On page 7813 of the specification, line 9, "copolymerized product" is amended to "copolymerized product".

(b) 1st to 2nd lines from the bottom of the chemical formula C of the fourth monomer on page 14] is corrected as follows.

"0M2= CH-COOCH,, CH20CI-12C
H2- or higher

Claims (1)

[Claims] (A) General formula (1) (wherein R"ldH or [CH, R2u-C)L
, CH20-. X is H, C1* Br+ CH, + CH30, C6H
5 or C6H5°, m represents an integer from 1 to 3, and 30 to 95% by weight of a polymerizable monomer or a mixture thereof in which R2 is represents H or CH3, R4 is -CH2
CH20-. Ar is divalent), all residues of enol LA n is 1 to 3
p represents an integer from 0 to 4, but is 0 and R4 is -Cf (if n = 2CHCH20-)
1H) or a mixture thereof O
~70M quantity, '(C) General formula (III) with a refractive index of 1.450 or more
)5? (CH2-C-COO←-R' (In) (wherein, R5
is represented by H or CH5', R6 represents a saturated aliphatic hydrocarbon group which may contain an ether, ester, or alcohol with a valence of q, and q represents an integer of 2 to 6). Monomer or polymerizable composition.