JPH1135611A - Resin composition, active energy line curing resin composition and its cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition curable with an active energy line such as ultraviolet rays or electron beam, providing a cured material excellent in durability and high in refractive index useful in an optical field, by including a specific (meth)acrylic acid ester, a photopolymerization initiator and a glycidyl ether. SOLUTION: This composition comprises (A) a (meth)acrylic acid ester containing a halogen-substituted phenyl group in the molecule, (B) a radical- based photopolymerization initiator, (C) a glycidyl ether containing a halogen- substituted phenyl group and (D) a cationic photopolymerization initiator. The amount of the component A used is 40-70 pts.wt. and that of the component C is 30-60 pts.wt. based on 100 pts.wt. of the total of the components A and C. The amount of the component B used is 1.0-3.0 pts.wt. based on 100 pts.wt. of the component A and that of the component D is 1.0-3.0 pts.wt. based on 100 pts.wt. of the component C. A radically polymerizable monofunctional monomer or polyfunctional monomer in an amount of 5 15 pts.wt. based on 100 pts.wt. of the component A may be used except the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which is cured by irradiation with an active energy ray such as an ultraviolet ray and an electron beam, and which can be used in the optical field to obtain a cured product having a high refractive index and excellent durability. .

[0002]

2. Description of the Related Art Conventionally, optical elements such as lenses, prisms and optical fibers are often made of glass, but may be made of plastic. Optical elements made of plastics are lighter than glass products, have excellent impact resistance, and can be easily mass-produced because of their ease of molding, and the demand for these elements has been increasing in recent years.
The resin composition used to make such an optical element needs to be colorless and transparent. As such a resin, a general-purpose resin such as a polystyrene resin, a polycarbonate resin, and an acrylic resin has been used.

[0003] As a method for producing a plastic used for these optical elements, a resin composition obtained by mixing a monomer, a peroxide as a polymerization initiator and other components as necessary is injected into a mold and heated and polymerized. A molding polymerization system was used. For example, JP-A-59-19391
No. 5 discloses di (meth) having a halogen-substituted aromatic ring.
A production method has been proposed in which a polymerization initiator such as a peroxide is mixed with an acrylate at a temperature higher than the melting point, and polymerization is started under heating and melting. However, in this manufacturing method, it is difficult to obtain a uniform cured product due to the influence of thermal distortion and the like, and there is a drawback in workability, such as filling a mold as powder. As described above, it is difficult to uniformly control the polymerization conditions in the production method using heat polymerization, and the reaction rate of the monomer is usually 70 to 70.
It was as low as about 80%.

On the other hand, in the method of curing by irradiation with light, in particular, irradiation with active energy rays such as ultraviolet rays and electron beams, the reaction can be freely controlled by controlling the active energy rays, and the heating is substantially performed. Since no means is required, accumulation of thermal strain due to a difference in thermal expansion between the resin composition and the cured product obtained by molding and molding can be avoided. For this reason, a cured product having excellent impact resistance is obtained, and the effect of preventing unevenness of the refractive index due to distortion inside the cured product is obtained.

[0005]

However, the cured products of these resin compositions have a refractive index in the range of 1.49 to 1.57, and glass having a wide refractive index of 1.4 to 1.9. By comparison, the range of refractive index that can be adjusted arbitrarily is narrow,
There was a problem that the refractive index was low. Even a polystyrene resin or a polycarbonate resin, which can obtain a cured product having a relatively high refractive index among the resin compositions, has a problem that it is difficult to increase the refractive index from 1.57. If the cured product does not have a high refractive index, the thickness of the lens must be increased in order to shorten the focal length of the lens, etc., and the light feature of plastic products cannot be used. Since the occupied space volume is large, it is difficult to reduce the weight and size of the optical component. A resin composition having a refractive index higher than 1.57 is disclosed in
184210 proposes a photocurable high refractive index resin composition comprising a di (meth) acrylate having a halogen-substituted aromatic ring. However, since this di (meth) acrylate is a powder, it must be diluted with a monomer such as styrene or vinyltoluene.
It is difficult to achieve a high refractive index of 60 or more, and if the resin composition is stored for a long period of time, the powder component of this di (meth) acrylate tends to precipitate, or the polymerization rate is slow, resulting in poor practicality. There were challenges.

The inventors of the present invention have conducted intensive studies to solve such problems, and as a result, as a diluting monomer of a (meth) acrylic acid ester having a halogen-substituted phenyl group in the molecule which is a powder, an intramolecular halogen-substituted phenyl group is used. By using a glycidyl ether having the formula (1), it can be cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and has excellent durability in the optical field, and a cured product having a high refractive index of 1.60 or more can be obtained. The knowledge that a resin composition can be provided has been obtained, and the present invention has been completed.

[0007]

That is, the present invention provides a (meth) acrylate (A) having a halogen-substituted phenyl group in the molecule, a radical photopolymerization initiator (B), and a halogen in the molecule. A resin composition comprising a glycidyl ether (C) having a substituted phenyl group and a cationic photopolymerization initiator (D), wherein the cured product has a refractive index of 1.60 or more. An active energy ray-curable resin composition characterized by comprising the resin composition, wherein the active energy ray-curable resin composition is a cured product of the active energy ray-curable resin composition. is there.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The (meth) acrylic acid ester (A) having an intramolecular halogen-substituted phenyl group used in the present invention is a (meth) acrylic acid having a phenyl group substituted with a halogen such as chlorine, bromine or iodine. It is an acid ester.

The component (A) includes 2,4,6-trichlorophenol acrylate, 2,4,6-tribromophenol acrylate, 2,4,6-trichlorophenol methacrylate and 2,4,6-tribromophenol. Monofunctional (meth) acrylates such as methacrylate, and 2,2'-bis (4-methacryloxyethoxy-3-chlorophenyl) propane, 2,2'-bis (4-methacryloxyethoxy-3-bromophenyl)
Propane, 2,2'-bis (4-methacryloxyethoxy-3,5-dibromophenyl) propane, 2,2'-
Bis (4-methacryloxydiethoxy-3,5-dichlorophenyl) propane, 2,2′-bis (4-methacryloxydiethoxy-3,5-dibromophenyl) propane, 2,2′-bis (4-acryl Roxyethoxy-3,
The halogen-substituted structure of bisphenol A such as 5-dibromophenyl) propane and 2,2′-bis (4-acryloxyethoxy-3,5-dichlorophenyl) propane, and an ethoxy group —CH ₂ CH ₂ O And a polyfunctional monomer converted into a (meth) acrylic acid diester through-. Among them, 2,4,6-tribromophenol methacrylate and 2,2′-bis (4-methacryloxyethoxy-3,5-dibromophenyl) are preferred because they are easily available and can have a high refractive index. Propane is preferred.

The amount of the component (A) used is preferably 20 to 80 parts by weight, more preferably 40 to 70 parts by weight, based on 100 parts by weight of the total of the components (A) and (C). If the amount is less than 20 parts by weight, there is a possibility that the refractive index of the cured product is low and physical properties are problematic, and the curing speed is reduced.
If the amount exceeds 80 parts by weight, the component (A) may precipitate or the hardness of the cured product may decrease when stored for a long period of time.

The radical photopolymerization initiator (B) used in the present invention is not particularly limited, and any known one may be used.

As the component (B), acetophenone-based
Benzoin-based, benzophenone-based, thioxanthone-based, and the like. As acetophenones, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2
-Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like. As a benzoin system,
Benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal and the like can be mentioned.
Benzophenones include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate and 3,3'-
Dimethyl-4-methoxybenzophenone and the like. As the thioxanthone, thioxanthone, 2,
4-diethylthioxanthone and 2,4-diisopropylthioxanthone. Of these, acetophenone-based and benzoin-based are preferred in terms of curing speed,
1-hydroxycyclohexyl phenyl ketone and benzyl dimethyl ketal are more preferred.

The amount of component (B) used is 100 parts of component (A).
It is preferably 0.5 to 5.0 parts by weight based on part by weight.
0 to 3.0 parts by weight is more preferred. If the amount is less than 0.5 part by weight, the curing speed may be reduced. If it exceeds 5.0 parts by weight, the component (B) may be precipitated when stored for a long time.

As the glycidyl ether (C) having a halogen-substituted phenyl group in the molecule used in the present invention, a halogenated phenyl glycidyl ether represented by the following formula (1) is preferable in terms of availability. Examples of the halogenated phenyl glycidyl ether represented by the following formula (1) include dibromophenol glycidyl ether and dibromophenol glycidyl ether.

Embedded image

The amount of the component (C) used is preferably 20 to 80 parts by weight, more preferably 30 to 60 parts by weight, based on 100 parts by weight of the total of the components (A) and (C). If the amount is less than 20 parts by weight, the component (A) may precipitate when stored for a long time. If the amount is more than 80 parts by weight, there is a possibility that the refractive index of the cured product is low, causing problems in physical properties, and the curing speed is reduced.

The cationic photopolymerization initiator (D) used in the present invention includes a triphenylsulfonium salt compound and an iron arene complex. Examples of the triphenylsulfonium salt compound include a mixture of an antimony compound and a phosphorus compound. Examples of antimony compounds include a mixture of triarylsulfonium hexafluoroantimonate salts. Examples of the phosphorus system include a mixture of a triarylsulfonium hexafluorophosphate salt and the like. Examples of the iron arene complex include (n-cyclopentadienyl) iron (1+) 6 fumaric acid. Among these, a triphenylsulfonium salt compound is preferable because it is easily available. Of the triphenylsulfonium salt compounds, antimony and phosphorus compounds are preferred.

The amount of component (D) used is 100% of component (C).
It is preferably 0.5 to 5.0 parts by weight based on part by weight.
0 to 3.0 parts by weight is more preferred. If it is less than 0.5 part by weight, the curability may be poor. If it exceeds 5.0 parts by weight, the compatibility with the resin composition may be reduced.

In order to improve the durability of the resin composition and the cured product used in the present invention, a radically polymerizable monofunctional monomer or polyfunctional monomer (E) other than the component (A) is used.
May be used as long as the object of the present invention is not impaired.
Further, the resin composition used in the present invention may be coated or adhered to an adherend such as glass or plastic. However, in order to improve the adhesion of the cured product, (E) )
The components may be used within a range that does not impair the purpose of the present invention. As the component (E), methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth)
Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, alkyloxy (poly) ethylene glycol mono (meth) acrylate, alkyloxy ( Poly) propylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, morpholine (meth) acrylate , Ethylene oxide-modified succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate,
Monofunctional (meth) acrylates such as tetrafluoropropyl (meth) acrylate and 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, polyethylene glycol di (meth) acrylate, polyglycerol di (meth) acrylate, ethylene oxide modified Bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth)
Such as acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate Compounds having an allyl group such as polyfunctional (meth) acrylate, diallyl acrylate, diallyl maleate, diallyl phthalate, triallyl isocyanurate and allyl glycidyl ether, tris (meth) acryloyloxyethyl isocyanurate, various epoxy (meth) acrylates , Various phenoxyethylene glycol mono (meth) acrylates, various urethane (meth) acrylates, styrene, divinylbenzene, α-
Methylstyrene, N-vinylcaprolactam, and
Examples thereof include alkyl vinyl ethers, and one or more of these may be used in combination. Of these, phenoxyethylene glycol mono (meth) acrylate and urethane (meth) acrylate are preferable, and urethane (meth) acrylate is more preferable, in terms of imparting flexibility and durability. Urethane (meth) acrylate is produced by reacting isocyanate, polyol and hydroxy (meth) acrylate. Examples of the production method include a method in which isocyanate and polyol are first reacted and then hydroxy (meth) acrylate is reacted, and a method in which isocyanate and hydroxy (meth) acrylate are first reacted and then polyol is reacted.

The amount of the component (E) used is 100 parts of the component (A).
It is preferably 20 parts by weight or less, more preferably 5 to 15 parts by weight based on parts by weight. If the amount is less than 5 parts by weight, the effect may not be obtained. If the amount exceeds 20 parts by weight, no further effect may be expected.

Also, (meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl phosphate, dioctyl 2- (meth)
Acryloyloxyethyl phosphate, diphenyl 2
-Use of a phosphate ester having a vinyl group or a (meth) acryl group such as (meth) acryloyloxyethyl phosphate and (meth) acryloyloxyethyl polyethylene glycol acid phosphate to improve adhesion to an adherend. Good. Further, within the range not impairing the object of the present invention, an antioxidant, a polymerization inhibitor, a stabilizer, a plasticizer, a thixotropy-imparting agent, a silane coupling agent,
Chelating agents, dyes, pigments, fillers, flame retardants, antistatic agents, surfactants and the like may be used.

The resin composition of the present invention usually contains no solvent, and can be easily produced by mixing raw materials to be used in a vessel equipped with a stirring device. The resin composition of the present invention can be cured by irradiating active energy rays such as ultraviolet rays and electron beams. Among the active energy rays, ultraviolet rays are preferred in terms of easy operation. As the ultraviolet irradiation device used at this time, a device equipped with a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like can be used. At the time of curing, it is preferable to cure in an atmosphere containing no oxygen such as nitrogen in order to achieve a high curing rate and good surface curing.

[0022]

The present invention will be described in more detail with reference to the following examples.

Example 1 A resin composition having the composition shown in Table 1 was prepared. Among the components shown in Table 1, each component except for the cationic photopolymerization initiator was put in a predetermined container, and stirred and mixed at 60 ° C. for 2 hours. After cooling to room temperature, a cationic photopolymerization initiator was added, and the mixture was further stirred and mixed for 1 hour to obtain a resin composition. Using the resin composition, physical properties were measured by the methods described below. The results are shown in Table 2.

[0024]

[Table 1]

[0025]

[Table 2]

Example 2 The procedure of Example 1 was repeated, except that a resin composition having the composition shown in Table 3 was prepared. The results are shown in Table 4.

[0027]

[Table 3]

[0028]

[Table 4]

Example 3 Example 3 was carried out in the same manner as in Example 1 except that a resin composition having the composition shown in Table 5 was prepared. The results are shown in Table 6.

[0030]

[Table 5]

[0031]

[Table 6]

Comparative Example 1 The procedure of Example 1 was repeated except that a resin composition having the composition shown in Table 7 was prepared. The results are shown in Table 8.

[0033]

[Table 7]

[0034]

[Table 8]

(Materials used) Brom-substituted bisphenol A diethoxylate dimethacrylate

Embedded image Methyl-substituted phenoxyethyl acrylate

Embedded image Phenoxy polyethylene glycol monoacrylate

Embedded image

(Measurement Method) [Properties of Curable Resin Composition] The condition was visually confirmed at 23 ° C. [Hardness of cured product] Cap-shaped mold made of polyethylene (about 20
(φ, thickness: 3 mm), and irradiate ultraviolet rays from both sides (ultraviolet irradiation amount: 4000 mj / c)
m ² ) to obtain a cured product. After standing for 24 hours in an atmosphere of 23 ° C. and a humidity of 65%, the hardness of the cured product was measured by using a spring hardness tester [Model H, manufactured by Kamishima Seisakusho Co., Ltd.] in the above atmosphere.
D-104N / model SHORED], and the measured value was used as the hardness of the cured product. [Refraction index of cured product] UV irradiation (UV irradiation amount: 400
0 mj / cm ² ) and left for 24 hours in an atmosphere of 23 ° C. and a humidity of 65% to obtain 10 mm × 10 mm ×
A cured product having a thickness of 3 mm was prepared and measured using an Abbe refractometer in a 25 ° C. atmosphere. [Curing time] It was measured by the fixing time. The resin composition was injected between two slide glasses, and 5.0 mw / cm ² by an ultraviolet lamp (BL-100 manufactured by Stanley Electric Co., Ltd.).
Under the following conditions. The time from the start of irradiation until the slide glass stopped moving by hand was defined as the fixing time. [Presence of Precipitation of Components During Storage] An appropriate amount of resin was placed in a transparent glass container, left in a cool and dark place (5 ° C. or lower) for 7 days, and the presence or absence of precipitate in the resin composition was observed.

[0037]

According to the resin composition of the present invention, a resin composition having excellent durability in the optical field, a refractive index of 1.60 or more can be provided, and no precipitation is observed even after long-term storage. The effect is obtained. For this reason, the optical parts can be reduced in weight and size, and can be stored for a long period of time.

Claims (4)

[Claims] 1. A (meth) acrylate (A) having a halogen-substituted phenyl group in a molecule, a radical photopolymerization initiator (B), and a glycidyl having a halogen-substituted phenyl group in a molecule. A resin composition comprising an ether (C) and a cationic photopolymerization initiator (D). 2. The resin composition according to claim 1, wherein the cured product has a refractive index of 1.60 or more. 3. An active energy ray-curable resin composition comprising the resin composition according to claim 1 or 2. 4. A cured product of the active energy ray-curable resin composition according to claim 3.