JPH0317107A - New clear resin, high-refractive index clear resin for optics, coating resin and monomer therefor - Google Patents

Abstract

PURPOSE:To obtain a clear resin which has excellent transparency and is useful for an optical material, a molding material, films, an optical fiber material and coatings. CONSTITUTION:The subject resin is produced by homopolymerization of a monomer of the formula (R is H, CH3) such as 1-acryloyloxydibenzofuran, or copolymerization thereof with another copolymerizable monomer such as styrene, methyl (meth)acrylate, methyl cinnamate.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to transparent resins, high refractive index transparent optical resins, paint resins, and monomers, and more specifically to optical materials, hollow-shaped materials, and optical fibers. Transparent resins that can be used for materials, films, paints, etc., transparent optical resins with high refractive indexes that are transparent and lightweight, resins for paints that have high refractive indexes and excellent transparency, and these. This invention relates to novel monomers that can be used as feedstock monomers during polymerization.

<Prior Art> In recent years, organic optical materials have attracted attention as materials for optical materials in place of the conventionally used inorganic glasses, and are rapidly being put into practical use. This is because organic optical materials are lighter, have better impact resistance, and are easier to process than inorganic glasses.
Because of its superior properties, and especially for safety reasons, organic optical materials are being used instead of inorganic glass for mirror lenses and the like. Organic optical materials currently in practical use are mainly homopolymers of polymethyl methacrylate and diethylene glycol bisallyl carbonate or copolymers with polyfunctional monomers.

However, the organic optical material has a low refractive index of around 1.5, and therefore, when used as a lens material for vision correction, for example, the thickness of the lens must be increased compared to inorganic glass to obtain the same power. However, it is not always possible to satisfy the demands of consumers for lighter weight and thinner thickness.

Therefore, there is a strong desire to develop organic optical materials that have a high refractive index, are transparent, and are lightweight.

On the other hand, in the field of paints, various studies are being conducted to improve the appearance performance of paint films, mainly automotive paints, such as adjusting the fluidity of paints during drying and curing, and reducing shrinkage of paint films. However, the reality is that sufficient attempts have not been made to increase the refractive index of the resin itself contained in paint compositions and improve the gloss of the paint film. The refractive index of the homopolymer of methyl methacrylate, butyl methacrylate, hexyl methacrylate, ethyl acrylate 1 or butyl acrylate is 1,490, 1,4, respectively.
83. 1.481, 1.469 or 1.466, and even the refractive index of a homopolymer of phenyl methacrylate or styrene, which is a monomer known as a high refractive index polymer, is 1.571 or 1.592, 1
．． The reality is that materials exceeding 600 are not used.

Therefore, there is a strong desire to develop resins for coatings that have a high refractive index and are transparent.

In general, the relationship between the chemical structure and refractive index of organic compounds is (IV
It is known that Tsucho・---
(IV)■ Where no: refractive index [R]: molecular refraction. [R] = 4π/3・NA・α(N
(A is the number of avocados, α is the polarizability) ■ = molecular volume V = M/ρ (M is the molecular weight, ρ is the density) Therefore, in order to increase the refractive index of a compound, molecular refraction [
Increase R]. That is, either a chemical structure with high polarizability is introduced or the molecular volume V is reduced. In other words, a method is being used to introduce atoms that increase the density.

Based on this point of view, several high refractive index organic optical materials have been studied mainly in the field of plastics, and the former organic optical materials with large molecular refraction [R] include halogen atoms such as chlorine and bromine, Alternatively, resins containing a large amount of aromatic rings and resins containing heavy metals such as lead, barium, and lanthanum have been developed as organic optical materials with a small molecular volume V.

However, among the above-mentioned organic optical materials, resins containing a large amount of halogen atoms have the disadvantage of poor weather resistance due to the chemical activity of the halogen atoms. However, there is a problem in that the melting point of the monomer increases and certain types of polymerizability deteriorate. On the other hand, resins containing heavy metals have the disadvantage that they have a high density and cannot be made lightweight, and the bonding points between metals and organic compounds are easily hydrolyzed, resulting in water resistance problems. .

<Problems to be Solved by the Invention> The main object of the present invention is to provide a transparent resin that can be used for optical materials, molded materials, optical fiber materials, films, paints, and the like.

Another object of the present invention is to provide a high refractive index transparent optical resin that is lightweight, has a high refractive index, and has excellent transparency.

Still another object of the present invention is to provide a coating resin that exhibits a high refractive index and excellent transparency.

Still another object of the present invention is to provide a highly polymerizable monomer that can be used as a feedstock monomer in the production of optical materials, molded materials, materials for optical fibers, films, paints, etc. .

According to the present invention, a homopolymer of a monomer represented by the following general formula (I) (wherein R represents H or CH.) or the monomer A transparent resin comprising a copolymer of a comonomer copolymerizable with a transparent resin is provided.

Further, according to the present invention, there is provided a novel method comprising a homopolymer of the monomer represented by the general formula (I) or a copolymer of a comonomer copolymerizable with the monomer. A high refractive index transparent optical resin is provided.

Furthermore, according to the present invention, there is provided a coating resin characterized by containing the above-mentioned homopolymer or copolymer. Furthermore, the present invention provides a monomer represented by the following structural formula (II).

Furthermore, the present invention provides a monomer represented by the following structural formula (Tl1).

The present invention will be explained in more detail below.

The monomer used as the raw material heptanomer for the transparent resin, high refractive index transparent optical resin, and paint resin of the present invention can preferably include the following general formula (I) R E cydibenzofuran, and in particular the following monomer: 2-methacrylicoxydibenzofuran and 2-methacrylicoxydibenzofuran represented by the structural formulas (I!) and (III) are completely new compounds, and can be used as the transparent resin and high refractive index transparent optical resin of the present invention. It also shows excellent performance as a monomer that is a raw material for paint resins. The structural formula (■) also shows the positional relationship of dibenzofuran.

(In the formula, R1 represents H or CH.)

Examples of the monomer represented by the general formula (!) used in the present invention include 1-acutyloxydibenzofuran, 2
-Acrylicyloxydibenzofuran, 3-Acrylicyloxydibenzofuran, 4-Acrylicyloxydibenzofuran, 1-methacryloxydibenzofuran, 2-
Methacryloxydibenzofuran, 3-methacrylicyloxydibenzofuran, 4-methacrylicyloxydibenzofuran, 4-methacrylicyloxydibenzofuran, 6 5 4 In addition, in polymerization, they can be used alone or as a mixture.

In the present invention, the monomers can be easily combined by combining known reactions. For example, it can be carried out by combining monomers represented by structural formulas (n) and (m) or by the following reaction formula.

R 1 (In the formula, R- represents H or CH3.) The raw material monomer for the transparent resin, high refractive index optical resin, and coating resin of the present invention is a monomer represented by the above general formula (summer). In addition, comonomers that can be copolymerized with the above monomer can be used. The comonomer is not particularly limited as long as it can be copolymerized with the monomer, and either a monofunctional monomer or a polyfunctional monomer can be used. Examples of the monofunctional monomer include vinyl aromatic comonomers such as styrene, chlorostyrene, 2,4-dichlorostyrene, promostyrene, 2,4-dibromostyrene, and vinylnaphthalene; methyl acrylate, ethyl acrylate; Butyl acrylate, octyl acrylate, phenyl acrylate, pendyl acrylate, chlorphenyl acrylate, dichlorophenylacrylate, trichlorphenyl acrylate, promophenyl acrylate, dibromophenyl acrylate,
7-acrylate comonomers such as tribromophenyl acrylate and β-naphthyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, pendyl methacrylate, chlorphenyl methacrylate, dichlorophenyl Methacrylate comonomers such as methacrylate, trichlorphenyl methacrylate, promophenyl methacrylate, dibromophenyl methacrylate, tribromophenyl methacrylate, β-naphthyl methacrylate; methyl cinnamate, phenyl cinnamate, chlorphenyl cinnamate, dichlorophenyl cinnamate , trichlorphenyl cinnamate, bromophenyl cinnamate, dibromophenyl cinnamate, tribromophenyl cinnamate, and other cinnamate ester comonomers; allyl benzoate, 2-chlorobenzoate allyl ester, phenyl allyl carbonate , allylic monomers such as 2-chlorophenylallyl carbonate, 2-promophenylallyl carbonate, dichlorophenylallyl carbonate, dibromophenylallyl carbonate, trichlorophenylallyl carbonate, tribromophenylallyl carbonate, and mixtures thereof, etc. It can be selected from the group consisting of: The polyfunctional monomer that is the comonomer includes, for example, aliphatic diol (meth)acrylic acid ester monomers such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and diethylene glycol dimethacrylate. allyl carbonate monomers of aliphatic diols such as ethylene glycol bisallyl carbonate and diethylene glycol bisallyl carbonate, divinyl aromatic compounds such as divinylbenzene, diallyl phthalate, diallyl isophthalate,
Diallyl esters such as diallyl terephthalate or their nuclear halides, hydroquinone diallyl carbonate, catechol diallyl carbonate, bisphenol A diallyl carbonate, 2,2'-bis(4-hydroxyethoxyphenyl)propane diallyl carbonate, bisphenol-(S) monodiallyl carbonate,
Diallyl carbonates such as bis(4-hydroxyethoxyphenyl) sulfone diallyl carbonate, thiobisphenol diallyl carbonate, bis(4-hydroxyethoxyphenyl) sulfide diallyl carbonate, or their nuclear halides, diacrylates of the above aromatic polyhydric alcohols Alternatively, it can be selected from the group consisting of dimethacrylates or their nuclear halides and mixtures thereof. Furthermore, in addition to the above-mentioned monomers or comonomers, 9t feedstock monomers that can be preferably used in the transparent resin and paint/use resin of the present invention include polyisocyanate compounds, amino resins such as alkyl etherified melamine formaldehyde resins; Other comonomers selected from a certain group of polyamine compounds, polycarboxylic acid compounds, etc., which have a functional group capable of reacting with a curing agent used in coating resins, etc., and which are copolymerizable with the above monomers. can be used.

Examples of the other comonomers include hydroxyl group-containing comonomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypipyracrylate, and hydroxypipyrmethacrylate; epoxy group-containing comonomers such as glycidyl acrylate and glycidyl methacrylate. Comonomer: Can be selected from a certain group of carboxyl group-containing comonomers such as acrylic acid, methacrylic acid, maleic acid, and mixtures thereof.

The resin used for the transparent resin, high refractive index optical resin, and coating resin of the present invention is selected from one or more monomers represented by the general formula (I) and polymerized, or It can be obtained by copolymerizing the monomer with one or more comonomers selected from a certain group of the above comonomers and other comonomers. At this time, the content ratio of the resin used is determined by the refractive index, hardness, mechanical strength such as toughness, glass transition temperature related to heat softening property, acid resistance, alkali resistance, etc. required for the desired application. Although it varies depending on the chemical resistance of the transparent resin, high refractive index optical resin, and coating resin as a whole, it is preferably 5 to 5.
100! It is desirable that the amount of a be in the range of 20 to 100% by weight, particularly preferably in the range of 20 to 100% by weight. As the polymerization or copolymerization method, a known radical polymerization method or photopolymerization method can be used, and examples of the radical polymerization method include bulk polymerization method, solution polymerization method, etc. It can be carried out by S suspension polymerization method, etc. Particularly when producing a molded body such as a mirror lens, a cast molding method using bulk polymerization method is preferable. Preferably legal.

Examples of the radical polymerization initiator used in the radical polymerization method include penzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxypiparate, and tart-butylperoxy-2-ethyl. Peroxides such as hexanoate, tart-butyl peroxybenzoate, acetyl peroxide, diisobutyl peroxydicarbonate, dicumyl peroxide, and azobisisobutyronitrile, azobis-2,4-dimethylbutyronitrile, dimethyl-2, It can be selected from one or more azobis compounds such as 2'-azobisisobutyrate. The content ratio of the radical polymerization initiator varies depending on the polymerization method, polymerization conditions, type of copolymerization, etc., but preferably the total monomer content is 10
It is desirable to use the amount in the range of 0.1 to 10 parts by weight relative to 0 parts by weight, and the polymerization temperature and polymerization time also depend on the component composition of the monomers used, the reactivity, and the type and use of the polymerization initiator. Although it varies depending on the amount, it is usually 1 to 1 at 10 to 150℃.
It is desirable to polymerize by reacting for 100 hours, and it is also possible to polymerize in multiple stages.

When producing an oval shaped body such as an eyeglass lens using the above photopolymerization method, a photopolymerization catalyst such as penzophenone, benzoin, A method in which benzoin methyl ether or the like is mixed, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the total monomers, and then irradiated with an ultraviolet lamp such as a high-pressure mercury lamp or heated with a hot air drying oven, etc. It is preferable to carry out the reaction at a polymerization temperature of 5 to 80° C. and a polymerization time of 1 to 100 hours. In this case, the radical polymerization initiator used in the above-mentioned radical polymerization method can also be used together.

In addition, when performing polymerization or copolymerization, for example, 2-hydroxy-4-n-octoxybenzophenone,
Adding ultraviolet absorbers such as penzotriazole substitutes, antioxidants such as hindered phenols and hindered amines, antistatic agents such as quaternary ammonium salts, and nonionic surfactants to improve practicality. is also possible.

The coating resin of the present invention can be used, for example, as a thermoplastic resin coating that dries and hardens by solvent volatilization, or as a thermosetting resin coating that is mixed with a curing agent.

In addition, as a paint form, it can be used as a clear paint that does not contain a colored pigment or the like, an enamel paint or a metallic paint that contains a colored pigment or an aluminum pigment, or the like. Furthermore, if necessary, UV absorbers such as 2-hydroxy-4-n-octoxybenzophenone and penzotriazole substitutes, antioxidants or light stabilizers such as hindered phenol and hindered amines, and surfaces such as silicone resins may be added. Various additives normally used in paints, such as regulators, curing catalysts, and fluidity regulators, can also be added. The manufacturing method, coating method and drying of these paints,
The curing method can be performed using known techniques depending on the required use.

In the coating resin of the present invention, when a coating film is formed by a photopolymerization method, the above monomer alone or a mixture of the above monomer and the above comonomer and/or other monomers is used. , using the high refractive index optical resin except that the polymerization time was 0.1 seconds to 30 minutes! The coating film can be formed in the same manner as in the production of mirror lenses and the like by photopolymerization.

Effects of the Invention The transparent resin of the present invention has excellent transparency;
Optical materials, shaped materials, films, materials for optical fibers,
It can be used for paints, etc. In addition, the high refractive index transparent optical resin of the present invention has a high refractive index and excellent transparency, so
It is particularly suitable for corrective eyeglass lenses. Furthermore, the coating resin of the present invention has a high refractive index and excellent transparency, which have conventionally been difficult to achieve from the coating resin itself.
It can be used for automobile paints, home appliance paints, metal paints, ultraviolet curing paints, and other paints where high gloss is desired. Furthermore, the monomer of the present invention has high polymerizability and is very effective as a material for obtaining the transparent resin, high refractive index transparent optical resin, and paint resin of the present invention.

<Examples> The present invention will be explained in more detail below using synthesis examples, examples, comparative examples, and test examples, but the present invention is not limited thereto.

1 ``Viewing'' 1 methacryloyloxy-induced ▲50m
The anhydrous ether of Q was cooled to -5°C, and then a solution consisting of 10 g of 2-hydroxydibenzofuran (manufactured by ROHNER Co., Ltd.) and 35 mQ of anhydrous ether and 8.6 g of anhydrous pyridine were added, and to this was added 11.3 g of methacryloyl chloride.
was added dropwise over 10 minutes. After the soaking was completed, the reaction was carried out at the same temperature for 30 minutes and then at room temperature for 2.5 hours, and then 50 mQ of water was added to terminate the reaction. The organic layer was extracted with ethyl ether, dried over anhydrous MgSO4, and then the solvent was removed.The product was then purified and separated by silica gel column chromatography to obtain 11g of 2-methacryloyloxydibenzofuran. The nuclear magnetic resonance (NMR) spectrum of the obtained compound is shown in Figure 1, and the infrared absorption (I
R) spectra are shown in FIG. 2. The position symbols added to FIG. 1 are as shown in the following formula.

▲20 mQ of anhydrous ether of Δ 2 Akkutyloxy was cooled to -5°C, and then a solution consisting of 5 g of 2-hydroxydibenzofuran (manufactured by ROHNER Co., Ltd.) and 10 mQ of anhydrous ether, and 1.59 M/12 n- 27.1+nQ of a hexane solution of butyllithium was added, and 3.7 g of acroyl chloride was added dropwise thereto over 5 minutes. The following procedure was followed in accordance with Example 1 to obtain 5 g of 2-acutyloxydibenzofuran. The NMR spectrum and IR spectrum of the obtained compound are shown in FIG. 3 and FIG. 4, respectively. The position symbols added to FIG. 3 are as shown in the following formula.

104L Next, the monomers synthesized in the above synthesis example and used in the following examples are abbreviated as shown below.

50.0 parts by weight of 2-MADBF as a monomer, 25.0 parts by weight of styrene as a monofunctional monomer, 25.0 parts by weight of divinylbenzene as a polyfunctional monomer, and 2.0 parts by weight of penzoyl peroxide as a polymerization initiator. 0 parts by weight were mixed and melted, poured into a lens casting frame consisting of two pieces of spherical glass and a gasket, and polymerized in a hot air heating oven at 90°C for 15 hours. After cooling, it was taken out from the mold and polymerized in the hot air heating furnace at 50°C for 4 hours and at 90°C for 1 hour.
After 5 hours, a transparent lens was obtained.

When the refractive index of this lens was measured using an Abbe refractometer, it was found to be . “It was 1.5992.

A transparent lens was produced by the same operating procedure as in Example 1, using monomers and copolymers of the types and amounts listed in Table 1, and using penzoyl peroxide as a polymerization initiator. I got it. Table 1 shows the refractive index of the obtained lens.

(The following is a blank space) 40AL 64.1 parts by weight of benzene was charged into a round bottom flask equipped with a stirrer, a dropping funnel, a thermometer, and a nitrogen introduction tube, and the mixture was refluxed at 80° C. under a nitrogen stream.

Next, 5 parts by weight of benzene. 2-MADBF 7.5 parts by weight, 2-ethyl hydroxy methacrylate 6.96 parts by weight, acrylic acid 0.18 parts by weight, methyl methacrylate 3
．． A mixed solution of 76 parts by weight of butyl methacrylate, 11.60 parts by weight of butyl methacrylate, and 0.90 parts by weight of azobisisobutyronitrile was added dropwise from the dropping funnel over 2 hours, and then reacted for 1 hour at the same temperature. A paint composition solution having a solid content of 30% by weight was obtained. The acid value and hydroxyl value of the obtained composition are:
Each 4.7KOH■/g. It was IOOKOH■/g.

A coating composition was obtained by the same procedure as in Example 7, except that the monomer in Example 7 was replaced with 2-AcDBF. The acid value and hydroxyl value of the obtained composition were It is shown in Table 2.

Co-linked IL-2i The essential components of the present invention were obtained using the same operating procedure as in Example 7, except that the types and amounts of the jlL mer and comonomer in Example 7 were changed as shown in Table 2. A conventional coating composition containing no component monomer represented by general formula (I) was obtained. Table 2 shows the acid value and hydroxyl value of the obtained composition.

Trial 1 4L 82.4 parts by weight of the paint composition solution obtained in Example 7 was added with the trade name "Yuban #220" (solid content 60% by weight, manufactured by Mitsui Toatsu Chemical Co., Ltd.) as a crosslinking agent.17. Add 6 parts by weight,
A paint assembly was obtained. The resulting coating composition was then diluted with xylene using a Ford Cup #4 for 20 seconds, and then spray-coated to a dry film thickness of 30 μm on a glass plate previously coated with black paint.
Baked at ℃ for 30 minutes.

The gloss value of the obtained coated plate consisting of 27Fl of the black coating film/one copy of the clear coating was measured using a Dori-gon variable angle gloss meter, trade name rD4 7R-6FJ. (Hunter company C stock)!
2). As a result, the Rs value was 95.3.0/I value was 98.0, which was a high value. Here, the Rs value is a 30° gloss value, and the D/I value is a value representing the sharpness of the coating film, and the higher the value, the better the sharpness. Test Th A coated plate was obtained using the same formulation and operating procedure as in the test example, except that the coating resin of Example 7 used in test example 1 was replaced with the resin shown in Table 3. DorL-go of the obtained coated plate
Table 3 shows the measured values using an n-angle gloss meter.

Since Test Examples 1 and 2 contained the coating resin of the present invention as a component thereof, they exhibited high image clarity, especially high Rs values. On the other hand, in Test Examples 3 and 4, it was found that because the conventional paint resin was used, the image clarity was inferior to that of the paint resin of the present invention.

[Brief explanation of the drawing]

Figure 1 is a chart showing the nuclear magnetic resonance (NMR) spectrum of 2-methacrylicoloxydibenzofuran obtained in Synthesis Example 1, Figure 2 is a chart showing its infrared absorption (IR) spectrum, and Figure 3 is a chart showing the synthesis Nuclear magnetic resonance (NMR) of 2-acroyloxydibenzofuran obtained in Example 2
A chart showing the spectrum, Figure 4 shows its infrared absorption (
2 is a chart showing an IR spectrum.

Claims (1)

[Claims] 1) A monomer represented by the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R- represents H or CH_3.) A transparent resin comprising a homopolymer or a copolymer of a comonomer copolymerizable with the monomer. 2) The following general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, R- represents H or CH_3.) Homopolymer of the monomer or the monomer 1. A high refractive index transparent optical resin characterized by containing a copolymer of a polymer and a comonomer that can be copolymerized. 3) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, R- represents H or CH_3.) Homopolymer of the monomer or the monomer 1. A coating resin comprising a copolymer of a monomer and a comonomer that can be copolymerized. 4) A monomer represented by the following structural formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) 5) Monomer shown by the following structural formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III)