JP2891557B2 - Epoxy acrylate resin molding material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material of an epoxy acrylate resin or an epoxy acrylate resin composition applicable to various optical uses such as eyeglasses, contact lenses and camera optical lenses.

[0002]

2. Description of the Related Art In recent years, transparent resins have been attracting attention as optical materials in addition to conventionally used inorganic glasses.
Due to its advantages such as light weight and impact resistance, its use as an optical lens for spectacles is increasing.

At present, resins practically used as optical lenses include polymethyl methacrylate resin, polydiethylene glycol bisallyl carbonate resin, polystyrene resin, polycarbonate resin, and the like.
Polymethyl methacrylate resin and polydiethylene glycol bisallyl carbonate resin are often used as resin lenses for eyesight correcting glasses.

However, since both polymethyl methacrylate resin and polydiethylene glycol bisallyl carbonate resin have low refractive indices of about 1.50, when these resins are used as a lens for correcting vision, it is necessary to use inorganic materials to obtain the same power. There is a disadvantage that the end thickness of the lens is larger than that of glass.

On the other hand, demands for lighter and thinner lenses are increasing from consumers, and development of a high-refractive-index transparent resin that enables this is expected.

In view of this, resins having a crosslinked structure have been proposed. For example, Japanese Patent Publication No. Sho 58-14449 discloses bis (3,5-dibromo-4-hydroxyphenyl).
Propane diacrylate or bis (3,5-dibromo-4-hydroxyphenyl) propane dimethacrylate is disclosed in JP-A-59-133221 and JP-A-60-1311.
No. 513 discloses a compound obtained by reacting a compound obtained by adding tribromophenyl glycidyl ether to acrylic acid or methacrylic acid with an isocyanate.
No. 1706 discloses a compound obtained by reacting a compound obtained by monoesterifying bis (3,5-dibromo-4-hydroxyphenyl) propane with acrylic acid and isocyanate, and JP-A-63-24201 discloses a hydroxy group. A compound obtained by reacting an aromatic compound containing glycidyl acrylate or glycidyl methacrylate with
JP-A-113007 proposes a resin using a compound obtained by ring-opening a halogenated phenylglycidyl ether with a hydroxy group-containing unsaturated ester.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molding material having a higher refractive index than conventional resins and having a higher heat resistance in terms of heat resistance.

[0008]

The present inventors have conducted studies to achieve the above object, and as a result, it has been found that a fluorene-based epoxy acrylate resin or a composition thereof is extremely easily cured by heat and has a high refractive index and a high refractive index. The present inventors have found that the molding material has a high surface hardness, and have reached the present invention.

That is, the present invention relates to an epoxy acrylate resin having a structure of the formula I

[0010]

[Formula I]

Wherein R represents H or a lower alkyl group, R ′ represents H or CH _3, and n is an integer of 0 to 20; an epoxy acrylate resin-based molding material, Further, the epoxy acrylate resin having the structure of the above formula I is used in an amount of 30 to 90% by weight of the whole composition.
And an epoxy acrylate resin-based molding material obtained by thermally curing a composition containing at least one other thermosetting compound in an amount of 70 to 10% by weight of the whole composition. Hereinafter, the contents of the present invention will be described in detail.

The epoxy acrylate resin of the formula I is an epoxy compound represented by the following formula II and having glycidyl ether at both terminals.

[0013]

[Formula II]

(Where R represents H or a lower alkyl group, R ′ represents H or CH _3, and n is an integer of 0 to 20) in a solvent such as cellosolve acetate;
It is synthesized by reacting with acrylic acid or methacrylic acid at 110 to 120 ° C. in the presence of a polymerization inhibitor such as hydroquinone using 2-ethyl-4-imidazole or triethylbenzylammonium chloride as a catalyst.

The obtained epoxy acrylate resin of the formula I is a solid having a softening point of about 50 to 60 ° C.

The production method of the epoxy compound of the formula II is the same as that of a general epoxy compound, and the diol of the following formula III is heated and melted in an equivalent amount of epichlorohydrin and reacted.

The acrylate component to be added to the terminal of the epoxy compound includes acrylic acid and methacrylic acid which can be polymerized by heat.

In addition, at the time of this addition reaction, hydroquinone, phenothiazine and the like may be added as a thermal polymerization inhibitor in an amount of several ppm to the epoxy compound.

In the present invention, the dihydric alcohol (diol) component present in the formulas I and II is derived from diols represented by the following formula III.

[0020]

[Formula III]

(However, R represents H or a lower alkyl group, and R ′ represents H or CH _3. ) These diol components are derived from diols used as raw materials, and give such diol components. The diols include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene and 9,9-bis (3-ethyl-4-hydroxyphenyl) Fluorene and the like.

As described above, the epoxy acrylate compound represented by the formula I has a characteristic that it can be liquid at a low temperature because of its low softening point. Therefore,
It is possible to produce a molded product by casting after melting.

The above relates to a molding material consisting solely of the epoxy acrylate resin of the formula I,
The epoxy acrylate resin represented by the formula I can also be used as an excellent molding material and coating material when other heat-curable compounds are used in combination.

The compounding ratio is preferably in the range of 10 to 50% by weight based on the whole composition. 1
If the amount is less than 0% by weight, the viscosity is too high to handle easily, and if it exceeds 50% by weight, heat resistance, adhesiveness and refractive index are reduced.

The other heat-curable compounds that can be used in combination in the present invention may be compounds having an unsaturated bond, such as compounds having an acryloyl group, compounds having a methacryloyl group, allyl compounds, and the like.
Examples thereof include unsaturated esters, unsaturated carboxylic acids, compounds having a vinyl group, and olefins, which may be in any form of a monomer, an oligomer, or a polymer.

Preferred are compounds having an acryloyl group and compounds having a methacryloyl group, that is, acrylates and methacrylates, and specific examples thereof include the following.

1) Compound having one acryloyl group or methacryloyl group in the molecule a) Aliphatic acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, allyl acrylate, butoxyethyl acrylate, butanediol monoacrylate, polyethylene Glycol acrylate, caprolactone acrylate, 2-cyanoethyl acrylate, and the like, and methacrylate compounds thereof.

B) Aromatic phenyl acrylate, benzyl acrylate, nonylphenoxy polyethylene glycol acrylate, phenoxyhydroxypropyl acrylate, and the like, and methacrylate compounds thereof.

C) Alicyclic cyclohexyl acrylate, dicyclopentanyl acrylate, alicyclic modified neopentyl glycol acrylate, dicyclopentenyl acrylate, isobonyl acrylate and the like, and methacrylate compounds thereof.

D) Phosphoric acid ester EO-modified phenoxylated phosphoric acid acrylate, EO-modified butoxylated phosphoric acid acrylate, EO-modified phosphoric acid acrylate, and the like, and methacrylate compounds thereof.

E) Others N, N-diethylaminoethyl acrylate, N, N-
Dimethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, and the like, and methacrylate compounds thereof. Vinyl acetate,
N-vinylcaprolactam, N-vinylpyrrolidone and the like.

2) Compound having two acryloyl groups or methacryloyl groups in the molecule a) Bisphenol bisphenol A diacrylate, EO modified bisphenol A diacrylate, EO modified bisphenol S diacrylate, EO modified bisphenol F diacrylate, etc. Those methacrylate compounds.

B) Aliphatic alcohol 1,4-butanediol diacrylate, dicyclopentanyl diacrylate, diethylene glycol diacrylate, ECH-modified ethylene glycol diacrylate, 1,6-hexanediol diacrylate, ECH
Modified 1,6-hexanediol diacrylate, long-chain aliphatic diacrylates, neopentyl glycol diacrylate, polyethylene glycol diacrylate,
Polypropylene glycol diacrylates and the like, and methacrylate compounds thereof.

C) Others ECH-modified phthalic acid diacrylate, EO-modified phosphoric acid diacrylate, metal diacrylate, and the like, and methacrylate compounds thereof.

3) Compound having three acryloyl groups or methacryloyl groups in the molecule a) Isocyanurate acrylated isocyanurate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, etc. Those methacrylate compounds.

B) Pentaerythritol-based dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like, and methacrylate compounds thereof.

C) Trimethylolpropane ditrimethylolpropane tetraacrylate, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, ECH-modified trimethylolpropane triacrylate, and methacrylates thereof Compound.

D) Others ECH-modified glycerol triacrylate, EO-modified phosphate triacrylate and the like, and methacrylate compounds thereof.

The epoxy acrylate resin and its composition in the present invention can be cured by heating alone to form a molded product, but can be cured and molded at any temperature by using a radical initiator.

As the radical initiator, known peroxide initiators and azobis initiators can be used. Examples of peroxide initiators are: 1) Ketone peroxides Methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone ketone peroxide, acetylacetone peroxide, etc.

2) Diacyl peroxide type isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, etc.

3) Hydroperoxides 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, etc.

4) Dialkyl peroxide dicumyl peroxide, 2,5-dimethyl-2,5-di-
(T-butylperoxy) -hexane, 1,3-bis (t
-Butylperoxy-isopropyl) benzene, t-butylcumyl peroxide, etc.

5) Peroxyketal 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-di- ( t-butylperoxy) -butane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, etc.

6) Alkyl perester 2,4,4-trimethylpentylperoxy-phenoxyacetate, α-cumylperoxy neodecanoate, t
-Butyl peroxybenzoate, di-tert-butyl peroxytrimethyl adipate, etc.

7) Percarbonate di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, etc.

8) Others Acetylcyclohexylsulfonyl peroxide,
t-butyl peroxyallyl carbonate, etc.

The following are examples of the azobis-based initiator.

1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (2,4-dimethylvaleronitrile) , 2,2'-azobis- (methyl isobutyrate),
2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), α, α'-azobis (isobutyronitrile), 4,4'-azobis- (4-cyanovaleic acid), etc.

[0050]

【Example】

[0051]

Example 1 Thermosetting molding material (epoxy acrylate resin) After pouring epoxy acrylate resin (I) (n = 0, R = H, the same applies hereinafter) liquefied by heating into a Teflon mold And heated in an oven at 240 ° C. for 1 hour to thermally cure.

FIG. 1 shows the result of thermogravimetric analysis of the cured product.
Table 1 shows the measurement results of the mechanical and thermal properties. Table 2 shows the results of measuring the light transmittance and the refractive index.

[0053]

Example 2 Thermosetting Molding Material (Epoxy Acrylate Resin) 1% by weight of dicumyl peroxide was added to 99% by weight of the same epoxy acrylate resin (I) as used in Example 1 which was melted by heating, and then Teflon was added. After being poured into a mold, the mixture was heated in an oven at 100 ° C. for 30 minutes and at 170 ° C. for 1 hour to be thermally cured. The physical properties of this cured product were the same as those of the cured product of Example 1.

[0054]

Example 3 Thermosetting molding material (epoxy acrylate resin composition) 33% by weight of the same epoxy acrylate resin (I) used in Example 1, 33% by weight of dipentaerythritol hexaacrylate, 33% by weight of pentaerythritol triacrylate Then, a composition obtained by sufficiently mixing 1% by weight of benzoyl peroxide as a radical initiator is poured into a Teflon mold, and the mixture is heated in an oven at 100 ° C. for 30 minutes.
Then, the mixture was heated at 150 ° C. for 1 hour and thermally cured.

FIG. 2 shows the result of thermogravimetric analysis of the cured product.
Table 2 shows the measurement results of the light transmittance and the refractive index. Table 3 shows the physical properties of the contact lens produced from the cured product.

[0056]

Example 4 Thermosetting molding material (epoxy acrylate resin composition) 66% by weight of the same epoxy acrylate resin (I) used in Example 1, 33% by weight of 2-hydroxyethyl methacrylate, and 1% by weight of benzoyl peroxide After pouring the composition obtained by mixing well into a Teflon mold, 1
Heating was performed in an oven at 00 ° C. for 30 minutes and at 150 ° C. for 1 hour to thermally cure.

Table 1 shows the results of measuring the mechanical and thermal properties of this cured product, and Table 2 shows the results of measuring the light transmittance and the refractive index. Table 3 shows the physical properties of the contact lens produced from the cured product.

[0058]

Example 5 Thermosetting molding material (epoxy acrylate resin composition) 49.5% by weight of epoxy acrylate resin (I), 49.5% by weight of ethylene glycol dimethacrylate, and 1% by weight of benzoyl peroxide were sufficiently mixed. The resulting composition was poured into a Teflon mold and heated in a 70 ° C. oven for 2 hours, 90 ° C. for 5 hours, and 120 ° C. for 3 hours to be thermally cured. The HDT of this cured product was 250 ° C.

[0059]

[Table 1]

[0060]

[Table 2]

Types of molding materials: a epoxy acrylate resin (I) b epoxy acrylate resin (I) 33% by weight dipentaerythritol hexaacrylate 33% by weight pentaerythritol triacrylate 33% by weight benzoyl peroxide 1% by weight c epoxy acrylate resin (I) 66% by weight 2-hydroxyethyl methacrylate 33% by weight Benzoyl peroxide 1% by weight

[0062]

[Table 3]

[0063]

According to the present invention, the epoxy acrylate resin represented by the formula I or the composition thereof is heat-cured to have excellent heat resistance, chemical resistance, high surface hardness, high refractive index and transparent molding. Material can be obtained.

This molding material can be applied to various optical uses such as glasses, contact lenses, and optical lenses for cameras.

[Brief description of the drawings]

FIG. 1 is a diagram showing a measurement result of thermogravimetric analysis in Example 1.
The horizontal axis indicates temperature (° C.), and the vertical axis indicates the degree of weight loss (%) with respect to the initial weight.

FIG. 2 is a view showing a measurement result of thermogravimetric analysis of Example 3.
The horizontal axis indicates temperature (° C.), and the vertical axis indicates the degree of weight loss (%) with respect to the initial weight.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08L 63:10 (56) References JP-A-3-106918 (JP, A) JP-A-4-268313 (JP, A) JP-A-5 JP-A-32807 (JP, A) JP-A-59-86616 (JP, A) JP-A-59-86615 (JP, A) JP-A-57-104901 (JP, A) JP-A-63-218725 (JP, A) Japanese Patent Publication No. 7-35426 (JP, B2) (58) Fields surveyed (Int. Cl. ⁶ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08G 59/00-59 / 72 C08J 5/00-5/24 G02B 1/00-1/12

Claims (2)

(57) [Claims] 1. An epoxy acrylate resin having the structure of the formula I (Where R represents H or a lower alkyl group, and R ′ is H
Or CH ₃ . n is an integer of 0 to 20. ),
Epoxy acrylate resin molding material cured by heat. 2. An epoxy acrylate resin having the structure of the formula I comprising from 30 to 90% by weight of the total composition, and at least one other heat-curable compound comprising 7% by weight of the total composition.
An epoxy acrylate resin-based molding material obtained by thermosetting a composition containing 0 to 10% by weight.