JPH10338725A - (meth)acrylate, resin composition using the same and its cured composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new (meth)acrylate capable of producing cured products excellent in heat resistance, surface hardness and impact resistance and having high refractive indexes and useful for resin compositions for lenses by reacting specific two sort of compounds with (meth)acrylic acid. SOLUTION: A compound expressed by formula I [R1 is H, methyl and ethyl; (a), (b) and (c) are each 1-4, the average of (a+b+c) is 3-12] is reacted with a compound expressed by formula II (R5 to R9 are each H, a 1-6C alkyl, a 1-6C alkoxyl, etc.; R10 is hydroxyl group or a halogen) to obtain the objective (meth)acrylate expressed by formula III [at least one of R2 to R4 is COCH=CH2 group or COC(CH3 )=CH2 group and the rest are groups of formula IV] in the presence of an esterifying catalyst such as p-toluene sulfonic acid, etc., and a solvent such as toluene, etc., preferably at 70-150 deg.C, then adding (meth) acrylic acid and reacting the mixture in the presence of the esterifying catalyst such as p-toluene sulfonic acid, etc., preferably at 70-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lens whose cured product is excellent in low specific gravity, high refractive index, surface hardness, chemical resistance, transparency, heat resistance, impact resistance, low water absorption and moldability. (Meth) acrylate suitable for a resin composition for use, a resin composition containing the same, and a cured product thereof.

[0002]

2. Description of the Related Art Lenses, especially plastic lenses,
Taking advantage of features such as easy molding and light weight, it is widely used for optical products. Among them, the mainstream of transparent plastics used as spectacle lenses is thermosetting plastics such as diethylene glycol bisallyl carbonate (for example, CR-39 manufactured by PPG). Important properties required for such plastic lenses include refractive index, moldability, heat resistance, impact resistance,
Low water absorption, excellent surface accuracy of molded articles, excellent dyeing properties, and the like. And in recent years, further improvement of these properties has been required, and various monomers replacing diethylene glycol bisallyl carbonate,
A method for producing a plastic lens using an oligomer has been proposed.

[0003]

In recent years, since diethylene glycol bisallyl carbonate has a low refractive index, many attempts have been made to develop a novel transparent plastic having a high refractive index. When trying to obtain a transparent plastic having a high refractive index, it is common to try to introduce a bromine group or an aromatic ring into the molecular structure of the resin composition for a plastic lens. However, this method has a problem that the obtained resin has difficulty in impact resistance and dyeability with a general disperse dye.

Japanese Patent Application Laid-Open No. 64-16813 discloses that
As a component for improving the impact resistance of a lens, di (meth) acrylates of polyalkylene glycols having an ether structure in the molecule are described. In addition, di (meth) acrylates of these polyalkylene glycols have high hydrophilicity, so that the dyeability of the lens is also improved.
Representative examples of di (meth) acrylate include polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. If such a di (meth) acrylate is used together with a monomer or oligomer having a bromine group and an aromatic ring, the impact resistance and the dyeability are improved. However, the more this is added, the lower the refractive index of the lens becomes, and furthermore, a problem arises in heat resistance and water absorption.

[0005]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies to find a solution for them, and as a result, by using a specific compound as a main component,
The present inventors have found a resin composition which is excellent in heat resistance, surface hardness and impact resistance and gives a cured product having a high refractive index, and has completed the present invention.

That is, the present invention relates to a (meth) acrylate (A) represented by the formula (1)

[0007]

Embedded image

(In the formula (1), R ₁ is a hydrogen atom, a methyl group or an ethyl group, and at least one of R ₂ , R ₃ and R ₄ is a —COCH ＝ CH ₂ group or —COC ( CH
₃ ) = CH ₂ group, and the rest of R ₂ , R ₃ and R ₄

[0009]

Embedded image

Wherein R ₅ , R ₆ , R ₇ , R ₈ and R
₉ is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a chlorine atom, a cyano group, a nitro group, a thiomethyl group, a phenyl group, a thiophenyl group or a naphthyl group; , C are each an integer of 1 to 4, and a +
The average value of b + c is an integer of 3 to 12. ) And a compound containing an unsaturated group (B) other than the component (A), a composition for a lens, and a cured product thereof.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. In the above formula (1), examples of the C ₁ -C ₆ alkyl group in R ₅ , R ₆ , R ₇ , R ₈ and R ₉ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,
n-butyl group, iso-butyl group, t-butyl group, n-
Examples include a pentyl group, an iso-pentyl group, an n-hexyl group, and an iso-hexyl group. Examples of the C ₁ -C ₆ alkoxy group include a methoxy group, an ethoxy group,
n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, n-hexoxy group,
Or an iso-hexoxy group.

The (meth) acrylate (A) represented by the above formula (1) is a compound represented by the formula (3)

[0013]

Embedded image

(In the formula (3), R ₁ , a, b and c are
It has the same meaning as above. A) a compound represented by the formula (4):

[0015]

Embedded image

(In the formula (4), R _{5 to} R ₉ have the same meaning as described above, and R ₁₀ represents a hydroxyl group or a halogen atom),
It can be obtained by reacting (meth) acrylic acid in any order. It is a known compound represented by the formula (3), and specific examples thereof include, for example,

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

And the like.

The reaction between the compound represented by the formula (3), the compound represented by the formula (4), and (meth) acrylic acid is carried out, for example, by first reacting the compound represented by the formula (3) with the compound represented by the formula (4) ) In the presence of an esterification catalyst such as p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid or sulfuric acid, preferably toluene, xylene,
In the presence of a solvent such as cyclohexane, n-hexane, n-heptane or a mixture thereof, preferably 70 to
The reaction is carried out at a temperature of 150 ° C. Specific examples of the compound represented by the formula (4) include, for example, o-methylbenzoic acid, m-
Methyl benzoic acid, p-methyl benzoic acid, 2,4-dimethyl benzoic acid, 3,5-dimethyl benzoic acid, o-methoxy benzoic acid, p-methoxy benzoic acid, p-ethyl benzoic acid, p-iso-propyl benzoic Acid, pt-butylbenzoic acid, pn-hexylbenzoic acid, p-iso-hexylbenzoic acid, p-ethoxybenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, 2,
4-dichlorobenzoic acid, p-cyanobenzoic acid, p-phenylbenzoic acid, p-nitrobenzoic acid, o-methylthiobenzoic acid, p-methylthiobenzoic acid, p-phenylthiobenzoic acid, 1-naphthoic acid, 2-naphthoic acid Acids and the like and acid halides thereof can be mentioned. Next, (meth) acrylic acid is added, and in the presence of an esterification catalyst such as p-toluenesulfonic acid, methanesulfonic acid or sulfuric acid,
Preferably, it can be obtained by reacting at a temperature of 70 to 150 ° C. The use ratio of the compound of the formula (3) is usually from 1.0 to 1 mol of the compound of the formula (2).
2.0 mol, preferably 1.0 to 1.2 mol. The use ratio of (meth) acrylic acid is 2.0-6.
0 mol, preferably 2.2 to 4.4 mol. The esterification catalyst is usually used in an amount of 0.1 to 15 parts by weight based on the total amount of benzoic acid or its derivative and (meth) acrylic acid used.
It is present at a concentration of 1 mol%, preferably 1 to 6 mol%.
The compound of formula (1) can be obtained as a single compound or as a mixture.

Specific examples of the component (B) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, n- (meth) acrylate
Butyl, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, (meth) ) N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, dibromopropyl (meth) acrylate, polyethylene glycol monoalkyl ether (meth) acrylate , Polypropylene glycol monoalkyl ether (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate ,
Phosphoethyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenyloxyethyl (meth) acrylate, tribromophenyloxyethyl ( (Meth) acrylate, tribromophenyloxy (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 4-phenylphenyl- 2-hydroxyoxypropyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, 1-
Naphthyl-2-hydroxypropyl (meth) acrylate, 2,4,6-tribromophenyl-2-methyloxyethyl (meth) acrylate, 2,4,6-trichlorophenyloxyethyl (meth) acrylate, 2,
Mono (meth) acrylate compounds such as 4,6-tribromophenyl-2-hydroxyoxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, tetrabutylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, trimethylo Rupuropantori (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta and hexa (meth)
Acrylate, tris (meth) acryloyloxyethyl isocyanurate, di (meth) acryloyloxyethyl isocyanurate, 2,2-bis (4- (meth) acryloyloxyethoxy-3,5-dibromophenyl) propane, bis (4- (Meth) acryloyloxyethoxyphenyl) sulfine, bis (4- (meth) acryloyloxyethoxy-3-phenylphenyl) sulfine, bis (4- (meth) acryloyloxyphenyl) sulfide, bis (4- (meth) acryloyloxy) Monofunctional to polyfunctional (meth) acrylate compounds such as diethoxyphenyl) sulfide and 2,4-di (meth) acryloyloxynaphthalene; styrene, chlorostyrene, bromostyrene, divinylbenzene, 1-vinylbenzene, 1-vinyl Vinyl compounds such as phthalene, 2-vinylnaphthalene and N-vinylpyrrolidone; allyl compounds such as diethylene glycol bisallyl carbonate, trimethylolpropane diallyl and diallyl phthalate; epoxy resins such as bisphenol type epoxy resin and novolak type epoxy resin and (meth) Epoxy (meth) acrylate compounds that are reactants of acrylic acid; organic polyisocyanates (eg, tolylene diisocyanate,
Xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) and a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol A reaction product of tri (meth) acrylate or the like; or the organic polyisocyanate, the hydroxyl-containing (meth) acrylate, and a polyol (for example, 2,2-bis (4-hydroxydiethoxyphenyl) propane, 2,2-bis ( 4-hydroxydiethoxyphenyl) sulfide, 2,2-bis (4-hydroxypentaethoxyphenyl) propane, 2,2
Urethane (meth) acrylate, which is a reaction product of -bis (4-hydroxydiethoxy-3,5-dibromophenyl) propane, polytetramethylene glycol, neopentyl glycol, polyester polyol, and the like. These can be used alone or in combination of two or more.

The mixing ratio of the component (A) and the component (B)
When the total amount of the component (A) and the component (B) is 100 parts by weight, usually 10 to 80 parts by weight of the component (A),
Component (B) is 90 to 20 parts by weight. Also preferably,
When the total amount of component (A) and component (B) is 100 parts by weight, component (A) 30 to 70 parts by weight, component (B) 70 to
The ratio is preferably 30 parts by weight. When the resin composition of the present invention is cured with an active energy ray such as visible light or ultraviolet light, a photopolymerization initiator can be added. Specific examples of the photopolymerization initiator that can be used include 2-hydroxy-
Examples thereof include 2-methyl-1-phenylpropan-1-one, hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and benzyldimethylketal. However, it is not limited to these. When curing with heat, a thermal polymerization initiator can be added. Specific examples of the thermal polymerization initiator that can be used include diisopropyl peroxydicarbonate, t-butyl peroxyisobutyrate,
Organic peroxides such as 1,3,3-tetramethylperoxy-2-ethylhexanoate and 2,2-azobis (2,
Azo compounds such as 4-dimethylvalernitrile) and azobisisobutyronitrile. These photopolymerization initiators and thermal polymerization initiators may be used alone or in combination of several types. The amount of these polymerization initiators used is
When the total amount of the component (A) and the component (B) is 100 parts by weight, usually 0.01 to 100 parts by weight of the total amount.
It is 10 parts by weight, preferably 0.1 to 5 parts by weight. Although the resin composition of the present invention can sufficiently achieve the intended purpose only with the above-mentioned components, the components (A) and (B) may be further modified so as not to change the original characteristics in order to further improve the performance. In addition to the polymerization initiator, it may contain additives such as an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a fluing agent, a pigment, a light stabilizer, an antistatic agent, a coupling agent, and organic solvents.

The resin composition of the present invention comprises the above (A)
It can be obtained by heating, mixing and dissolving (B) and the photopolymerization initiator.

The cured product of the resin composition of the present invention can be obtained by curing the resin composition of the present invention by irradiation with ultraviolet rays or electron beams, or by heat.

The resin composition of the present invention is particularly useful as a resin composition for lenses.
It can also be used for paints, coatings, gloss, adhesives and the like. The resin composition for lenses of the present invention is useful as a plastic lens material.

A plastic lens using the resin composition for a lens of the present invention is made into a mold made of a gasket made of polyvinyl chloride, ethylene-vinyl acetate copolymer or the like and two glass molds having a desired shape. It can be obtained by injecting the resin composition for a lens of the present invention into the resin, irradiating the resin composition with heating or an active energy ray, or by performing a combination thereof to cure the composition.

[0029]

The present invention will be described more specifically below with reference to examples and comparative examples. In the following, parts mean parts by weight.

Embodiment 1 Equation (5)

[0031]

Embedded image

358 parts of the compound represented by the following formula, 154 parts of p-phenylbenzoic acid, 440 parts of toluene and 26 parts of p-toluenesulfonic acid are charged and heated and refluxed. It was quantified and fractionated with a vessel. 1 generated water
When 6 parts were reached, the reaction mixture was cooled. The reaction temperature was 120-130 ° C. Further, 112 parts of acrylic acid, 3 parts of hydroquinone, and 10 parts of p-toluenesulfonic acid were charged into the reaction mixture, and the mixture was heated to reflux. The produced water was azeotroped with the solvent in the same manner as described above, and the water was quantified and collected by a water content receiver. The reaction mixture was cooled when the produced water reached 24 parts. The reaction temperature was 115-130 ° C.
The reaction mixture was dissolved in 1200 parts of toluene and 20% Na
After neutralization with OH aqueous solution, 20% NaCl aqueous solution 100
The part was washed three times. The solvent was distilled off under reduced pressure to obtain 480 parts of the acrylate (A-1) of the present invention represented by the formula (6).

[0033]

Embedded image

(In the formula (1), at least one of R ₁ , R ₂ and R ₃ is an acryloyl group, and the rest is p-
It is a phenylbenzoylcarboxy group. The compound represented by the formula (6) is a pale yellow transparent highly viscous liquid, has a viscosity (25 ° C.) of 1320 Pois, and has a refractive index (2
(5 ° C.) was 1.595. The compound represented by the formula (6) was obtained as a mixture, and the composition was analyzed.
86 mol% of a compound obtained by condensing 1 mol of p-phenylbenzoic acid with respect to 1 mol of the compound represented by the formula (5) represents 7 mol% of a compound obtained by condensing 2 mol of p-phenylbenzoic acid. The compound which was not present was 7 mol%.

The structure of the compound represented by the formula (6) was confirmed by proton decoupling using tetramethylsilane as a reference substance and deuterated chloroform as a solvent.

Embodiment 2 Equation (7)

[0037]

Embedded image

345 parts of the compound represented by the following formula, 86 parts of 1-naphthoic acid, 440 parts of toluene and 6 parts of p-toluenesulfonic acid were charged and heated and refluxed.
It was quantified and fractionated by a moisture quantification receiver. When the product water reached 9 parts, the reaction mixture was cooled. Reaction temperature is 120-13
It was 0 ° C. Further, acrylic acid 88 was added to the reaction mixture.
, 2 parts of hydroquinone and 7 parts of p-toluenesulfonic acid, and heated and refluxed. The produced water was azeotroped with the solvent in the same manner as described above, and the water was quantified and collected by a water content receiver. When the product water reached 19 parts, the reaction mixture was cooled. The reaction temperature was 115-125 ° C. Hereinafter, in the same manner as in Example 1, the acrylate of the present invention represented by the formula (8) (A-
2) 374 parts were obtained.

[0039]

Embedded image

(In the formula (1), at least one of R ₁ , R ₂ and R ₃ is an acryloyl group, and the remainder is 1-
It is a naphthoyl group. )

The compound represented by the formula (8) is a pale yellow, transparent and highly viscous liquid having a viscosity (25 ° C.) of 443 Pois.
The refractive index (25 ° C.) was 1.579. Expression (8)
Is obtained as a mixture, and the composition thereof is analyzed.
74 mol% of a compound obtained by condensing 1 mol of naphthoic acid, 2
The mole-condensed compound was 13 mol%, and the non-condensed compound of 1-naphthoic acid was 13 mol%. The structure of the compound represented by the formula (8) was confirmed in the same manner as in Example 1.

Examples 3 to 6, Comparative Example 1 A resin composition for a lens according to the present invention was prepared according to the composition shown in Table 1 (the number in the column of “composition” in the table is part by weight), and then adjusted to 50 mmHg. Depressurized and degassed at 25 ° C. for 30 minutes. Next, two pieces of tempered glass having a length of 100 mm, a width of 100 mm, and a thickness of 5 mm are opposed to each other at a distance of 2 mm, and the above composition is placed in a mold constituted by surrounding the periphery with a tubular gasket made of polyvinyl chloride. Except for Example 6, the mixture was heated and heated from 40 ° C. to 100 ° C. over 20 hours to cure. Example 6 is 20 cm from both sides of the mold.
UV light was irradiated from a 120 W / cm high pressure mercury lamp at a distance of 5 minutes for curing. Thereafter, the cured product is released from the mold, and 120 to remove internal strain of the cured product.
C. for 2 hours to obtain a transparent cured product of the present invention.
Using this cured product, the visible light transmittance (%), refractive index, Rockwell hardness, Tg (° C.)
The chemical resistance and specific gravity were measured.

Test method: Visible light transmittance (%): ASTM D 1003-6
1 was measured.屈折 Refractive index: The refractive index at 25 ° C. at 589.3 nm D-line was measured with an Abbe refractometer. -Rockwell hardness: measured according to JIS K7202. -Tg (° C): The glass transition temperature (Tg) was measured by a thermomechanical analyzer (TMA). O Chemical resistance: The surface of the cured product was wiped 20 times with absorbent cotton impregnated with methyl ethyl ketone, and changes in the surface of the cured product were observed. Judgment was made as “○” when no change in the surface of the cured product was observed, “△” when a linear streak was observed on the surface, and “×” when the surface was dissolved. Specific gravity: Measured according to JIS K7112.

[0044]

Table 1 Example Comparative Example 3 4 5 6 1 ○ Composition (A) Component Acrylate compound (A-1) 70 60 obtained in Example 1 Acrylate compound (A-2) 60 obtained in Example 2 60 (B) component Styrene 30 20 20 o-biphenyl methacrylate 20 20 phenyl methacrylate 20 20 other 1,1,3,3-tetramethylperoxy-2-ethylhexanoate 0.1 0.1 0.1 t-butylperoxyisobutyrate 0.05 0.05 0.05 0.1 Diisopropyl peroxydicarbonate 2.5 Methylphenylglyoxylate 0.1 1-Hydroxycyclohexylphenyl ketone 0.1 Diethylene glycol bisallyl carbonate 100 ○ Physical properties Visible light transmittance (%) 89 90 91 92 92 Refractive index 1.587 1.594 1.566 1.568 1.504 Rockwell hardness 96 96 98 96 95 Specific gravity 1.15 1.17 1.23 1.25 1.32 Glass transition temperature (℃) 96 94 90 93 80 Chemical resistance ○ ○ ○ ○ ○

As is clear from the above evaluation results, the cured product of the present invention is excellent in surface hardness, chemical resistance, and transparency, and has a high refractive index and a low specific gravity.

[0043]

According to the present invention, there is obtained a resin composition containing a novel (meth) acrylate which is excellent in surface hardness, chemical resistance and transparency, and provides a cured product having a low specific gravity and a high refractive index. Was. This resin composition is particularly useful as a resin composition for lenses.

Claims (4)

[Claims] 1. A (meth) acrylate (A) represented by the formula (1): (In the formula (1), R ₁ is a hydrogen atom, a methyl group or an ethyl group, and at least one of R ₂ , R ₃ and R ₄ is —COCHＣＨCH ₂ group or —COC (CH ₃ ) = CH ₂
And the rest are R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a chlorine atom, a cyano group, a nitro group, a thiomethyl group , A phenyl group, a thiophenyl group or a naphthyl group;
b and c are integers of 1 to 4, respectively, and the average value of a + b + c is an integer of 3 to 12. 2. A resin composition comprising a (meth) acrylate (A) represented by the formula (1) and an unsaturated group-containing compound (B) other than the component (A). 3. A resin composition for lenses comprising (meth) acrylate (A) according to claim 1, and a compound (B) containing an unsaturated group other than the component (A). 4. A cured product of the resin composition according to claim 1 or 2.