JPH0347817A - Transparent resin having high hardness - Google Patents

Abstract

PURPOSE:To provide the subject resin composed of a crosslinked polymer produced by copolymerizing a combination of two specific kinds of monomers, having high surface hardness and excellent transparency, chemical resistance, etc., and useful as a crazing material, optical lens. etc. CONSTITUTION:The objective resin can be produced by combining (A) a monomer of formula I {R is aliphatic or alicyclic residue which may contain a functional group of formula II, formula III, formula IV or formula V [(IP-O)<-> is isopropenylphenoxy group which is not included in R] bonded to isopropenylphenoxy, aliphatic residue having at least one alicyclic group, heterocyclic group, aromatic group or hetero atom in the residue or group of formula VI; n is integer of 1-4} and (B) a monomer having one or more kinds of m functional groups selected from the groups of formula VII, formula VIII and formula IX (n+m is integer of >=3) and radically polymerizing the monomers with heat, ultraviolet radiation, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a transparent resin that has high surface hardness, excellent scratch resistance, heat resistance, and chemical resistance, and a transparent resin made of the resin. Related to glazing materials, protective covers for discless devices, optical lenses, and hard coat materials.

[Conventional technology]

Traditionally, methacrylic resin, polycarbonate resin, polystyrene resin, etc. have excellent transparency, impact resistance, processability, and mass productivity, so they are used for windows of vehicles, residences, schools, sports facilities, etc., veranda wainscoting, balconies, etc. It is also used as a glazing material, protective covers for display devices such as various instrument panels, computer displays, LCD TVs, and vending machine front panels, optical lenses, lighting cover signs, safety glasses, optical disk substrates, etc. . Applications to these applications include glazing materials, protective covers for display devices, optical lenses, etc., in addition to their transparency, optical properties, mechanical strength, and rigidity, as well as their visibility, aesthetics, etc. High surface hardness and, in some cases, chemical resistance, heat resistance, etc. are required.

However, the above-mentioned general-purpose transparent resins have a linear polymer structure, so they do not have sufficient surface hardness, chemical resistance, or heat resistance. Even those coated with a hard coat cannot necessarily be said to have sufficient performance.

In order to solve these problems, diethylene glycoldiallyl carbonate resin and urethane polyacrylic ester (Japanese Patent Application Laid-Open No. 61-3610, Japanese Patent Application Laid-open No. 63-7502)
Transparent resins made of polymers having a crosslinked structure have been proposed, such as Japanese Patent Publication No. 2).

[Problem to be solved by the invention]

However, the above resins polymerize allyl groups, acrylic groups, and methacrylic groups with similar polymerization rates, making it difficult to control polymerization and easily causing runaway reactions, resulting in polymers with good surface conditions and little polymerization distortion. There are problems such as the long time required.

The purpose of the present invention is to provide easy control of polymerization, high surface hardness,
Another object of the present invention is to provide a transparent resin that can also have excellent chemical resistance and heat resistance.

[Means to solve the problem]

The present inventors conducted extensive research to solve the above problems.

As a result, by combining an isopropenylphenyl group as a polymerizable group with a slow polymerization rate and a polymerizable group with a faster polymerization rate, in other words, a compound having one or more isopropenylphenyl groups in one molecule and an isopropenylphenyl group By copolymerizing compounds with acryloyl groups, methacryloyl groups, and vinylphenyl groups that have high reradical polymerizability, runaway reactions during polymerization can be easily controlled, making it possible to significantly shorten polymerization time. We have found that not only this, but also a transparent resin with high surface hardness made of the crosslinked polymer of the present invention can be obtained.

In addition, this resin has high surface hardness, i.e., scratch resistance, and can be made to have heat resistance and chemical resistance, so plate-like polymers made of this resin can be used in vehicles, homes, schools, sports facilities, etc. Lenticular polymers are useful as glazing materials for windows, veranda wainscoting, balconies, etc., protective covers for display devices such as various instrument panels, computer displays, LCD televisions, and vending machine front panels, and as optical lenses. I found out. In addition, various resins, metals,
It has been found that a polymer coated onto a base material such as wood and polymerized is also useful as a coating film having scratch resistance and chemical resistance, that is, a hard coat material.

That is, the present invention provides (1) a monomer (A) represented by the following general formula (1), and a group ((IP-0+ represents an isopropenylphenoxy group and is not included in R) or bonded to the propenylphenoxy group (wherein R was bonded to the isopropenylphenoxy group (
IP-0)-C-N- group, (IP-0)-C-N- group,
II I
II 10H5H (IP-0)-C-0- group, (IP-0)-C- group monocarbonate 11 Aliphatic residue with or without selected functional group ((I
P-0+ represents an isopropenylphenoxy group and is not included in R) or (IP-0)-C-N- group, (IP-0)-C-N- group bonded to the isopropenylphenoxy group , II I
II 10H5H (IP-0)-(, -0- group, (IP-0)-C- group I
I
Alicyclic residue OH5H with or without a functional group selected from II (IP-0)-C-0- group, with or without a functional group selected from (IP-0)-C- group, Alicyclic group in the residue,
Aliphatic residues having at least one type selected from the group consisting of heterocycles, aromatic rings, and heteroatoms (nitrogen atoms, sulfur atoms, oxygen atoms, etc.) ((I'P-0+ represents an isopropenylphenoxy group; R ) or ■-
represents a C-group, and n represents an integer of 1 to 4; ) CH in one molecule
2=CH-C-0- group, a monomer (B) having m pieces of one type of functional group is combined and copolymerized so that (n+m) is an integer of 3 or more. High hardness transparent resin.

(2) High hardness and transparency consisting of a crosslinked polymer containing structural units represented by the following general formula (n) and/or (m) consisting of monomer (A) and monomer (B) of (1) resin.

(In the formula, R is bonded to the isopropenylphenoxy group (
IP-0)-C-N- group, (IP-0)-C-N- group,
II I
II 10H5H Aliphatic residues with or without a functional group selected from (IP-0)-C-0- group, (IP-0)-C- group ((IP
-0+ represents an isopropenylphenoxy group and is not included in R) or (IP'-0)-C-N- group bonded to the isopropenylphenoxy group, (IP-0)-C-N-
Group, II I
II 10HSH o 0 Alicyclic residues with or without functional groups ((
IP-0+ represents an isopropenylphenoxy group and is not included in R) or (IP-0)-C-N- group, (IP-〇)-C-N- group bonded to the isopropenylphenoxy group , 1 D II + 1 0H5H (IP-0)-C-0- group, (IP-0)-C- group II
with or without a functional group selected from 11, an alicyclic group in the residue,
Aliphatic residues having at least one type selected from the group consisting of heterocycles, aromatic rings, and heteroatoms (nitrogen atoms, sulfur atoms, oxygen atoms, etc.) ((IP-0+ represents an isopropenylphenoxy group; R represents (3)
Glazing material (4) made of the highly hard transparent resin described in (1) above; Protective cover for a display device (5) made of the highly hard transparent resin described in (1) above; Optical material made of the highly hard transparent resin described in (1) above. lens.

(6) A hard coat material made of the highly hard transparent resin described in (1) above.

(7) The following general formula (IV) (V) (VI)
(■) (■) (■) At least one monomer (A) selected from the group consisting of monomers represented by (■) and one type of CH2-CH-C-0 group in one molecule. Monomer (B) having m functional groups (n0m)
A high-hardness transparent resin made of crosslinked polymers that are copolymerized by combining them so that they become an integer of 3 or more.

The positions represent o, m, and p positions. ) H H (In the formula, n=1.R is -CH, -C2H5°, and the positions of the substituents on the aromatic ring are O, m, and p.) The positions are shown in the table. Furthermore, the position of the substituent on the aromatic ring is 01m.

Represents p-position. ) (In the formula, n=2.R is (CH2)3 (CH2 (CH2 (CH) represents -, -(CH2)6-.

Further, the positions of substituents on the aromatic ring are o-, m-, and p-positions.

) The positions of the substituents are o, m, p represents rank. ) represents. Furthermore, the position of the substituent on the aromatic ring is 01m.

Represents p-position. ) The monomer (A) of the present invention is represented by the following general formula (I).

3CCH3 (wherein R is bonded to the isopropenylphenoxy group (
IP-0)-C-N- group, (IP-0)-C-N- group,
II I
11 10H5H (IP-0)-C-0- group, (IP-0)-C- group to II
II Aliphatic residues with or without selected functional groups ((
I P-0+ represents an isopropenylphenoxy group, and R
) or (IP-0)-C-N- group bonded to isopropenylphenoxy group, (IP-0)-C-N- group, II I
II 10H5H (IP-0)-C-0- group, (IP-0)-C- group II

Alicyclic residues with or without functional groups selected from IIOO ((
rp-o+ represents an isopropenylphenoxy group and is not included in R) or (IP-0)-C-N- group, (IP-0)-C-N- group bonded to the isopropenylphenoxy group , Ill 1
110H5H (IP-0)-C-0- group, (IP-0)-C- group II
I
Alicyclic groups, heterocycles, aromatic rings, and heteroatoms (nitrogen atoms,
an aliphatic residue having at least one kind selected from the group consisting of sulfur atoms, oxygen atoms, etc. ((IP-0+ represents an isopropenylphenoxy group and is not included in R), or
(2) represents a -C- group, and n represents an integer of 1 to 4; ) The monomer (A) of the present invention is isopropenylphenol;
-N that reacts with the phenolic hydroxyl group of the compound
GO group, -NC8 group, -COOH group, -COC1 group, -
COBr group, halogenated alkyl group, -803R1 group (
R' is one to four functional groups selected from alkyl groups, aliphatic residues, alicyclic residues, or alicyclic groups, heterocycles, aromatic rings, and heteroatoms (nitrogen atoms, sulfur atoms, etc.) in the residues. A compound having an aliphatic residue having at least one aliphatic residue selected from the group consisting of atoms, oxygen atoms, etc.), or a compound obtained by reacting isopropylphenol with phosgene; more specifically, isopropenylphenol Carbamate ester compounds, carbamate thioester compounds, -COOH groups, -coc i obtained by the reaction of the phenolic hydroxyl group possessed by -NGO groups, -NC8 groups
group, ester compound obtained by reaction with ~COBr group, -COCl group, carbonate compound obtained by reaction with phosgene, halogenated alkyl group, -8O3R' group (
R' is an alkyl group or an aryl group.

Furthermore, although the organic group R in the above general formula (I) depends on the steric rigidity, etc., in general, the lower the molecular weight, the more preferable it is, and those with a residue moiety having a molecular weight of 15 to 500 are preferably used. .

Therefore, -NCO group, -NCS group, -CO group, which can react with the phenolic hydroxyl group of isopropenylphenol used when producing monomer (A) by the above method.
OH group, -COCl group, -COBr group, halogenated alkyl group, -5o3R' group (R' is an alkyl group or aryl group), alicyclic group, heterocycle, aromatic ring, and heteroatom (nitrogen A compound having an aliphatic residue having at least one aliphatic residue selected from the group consisting of atom, sulfur atom, oxygen atom, etc.) or phosgene is, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, cyclohexyl isocyanate. , methylisothiocyanate, ethylisothiocyanate, propylisothiocyanate, butylisothiocyanate, cyclohexylisothiocyanate, hexamethylene diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1゜2-dimethylcyclohexane-ω,ω′-diisocyanate, Isophorone diisocyanate, dicyclohexylmethane-4,
4'-diisocyanate, lysine diisocyanate,
Xylylene diisocyanate, phenylene bis(isopropylisocyanate), 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, bicyclo Hebutane triisocyanate, hexamethylene diisothiocyanate, cyclohexane diisothiocyanate, etc.

Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, phenylacetic acid, malonic acid, succinic acid, itaconic acid, maleic acid, fumaric acid, glutaric acid, glutaconic acid, adipic acid, pimelic acid, speric acid, azelaic acid Acid, sebacic acid, cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, pinic acid, homopicic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, phenylenediacetic acid, oxydiacetic acid, oxaadipic acid, thioniacetic acid, thiodipropionic acid, dithioniacetic acid, Dithiopropionic acid, and their acid chlorides, acid bromides, etc.

Diethylene glycol dichloroformate, phosgene, etc.

Iodomethane, bromomethane, chloromethane, iodoethane, bromoethane, chloroethane, iodopropane,
Bromopropane, chloropropane, iodobutane, bromobutane, chlorobutane, iodopentane, bromopentane, chloropentane, iodohexane, bromohexane, chlorohexane, iodohebutane, bromoheptane, chlorohebutane, iodooctane, bromooctane,
Chloroctane, iodocyclopenkune, bromocyclopentane, chlorocyclopentane, iodocyclohexane, bromocyclohexane, chlorocyclohexane, benzyl chloride 1. Dimethyl sulfate, diethyl sulfate, P
-Toluenesulfonic acid methyl ester, P-toluenesulfonic acid ethyl ester, short ethane, dibromoethane, dichloroethane, short propane, dibromopropane, dichloropropane, short butane, dibromobutane, dichlorobutane, short pentane, dibromopencune, dichloropene Short hexane, dibromohexane, dichlorohexane, bromochloroethane, bromochloropropane, chloroiodopropane, bromochlorobutane, bromochloropentane, bromochlorohexane, α, α′ -dibromoxylene, α, α′
- dichloroxylene, etc. are used. To obtain carbamate ester compounds, carbamate thioester compounds, ester compounds, carbonate compounds, and ether compounds using these, NCO groups, NC8 groups, -COOH groups, - COCl group, -COBr group, halogenated alkyl group, -3o3R' group (R' is an alkyl group or aryl group), have alicyclic groups, heterocycles, aromatic rings, and heteroatoms (nitrogen atoms, sulfur atoms) in the main chain. , oxygen atoms, etc.) or by reacting phosgene with isopropenylphenol by a conventionally known method. When a solvent is used, the solvent is distilled off after the synthesis reaction. Further purification is performed as necessary to obtain monomers (
As A), prepare for the next radical polymerization.

Specifically, the monomer (A) has the following general formula (% formula %) Examples include compounds such as

(In the formula, n=l, R is -CH, -C2H5°, and the positions of the substituents on the aromatic ring are o, m, and p.) The positions of the substituents on the aromatic ring are as follows.

) show the rank The positions are o, m, p represents rank. ) (In the formula, n=2.R is C-CH,,-C.

(In the formula, n-1, R is -C-N-CH3゜■ Sodium H C-N-C2H5゜ H OHOHOH represents. Further, the positions of the substituents on the aromatic ring are o and m.

Represents p-position. ) The positions of the substituents are o, m, p represents rank. ) (In the formula, n=2.R is (CH2)3 (CH2)5 (CH2)2 (CH2)4 (CH2)8 represents.

represents. Furthermore, the position of the substituent on the aromatic ring is 02m.

Represents p-position. ) Next, in the present invention, the monomer (B) having m CH2=CH-C-0- groups and one type of functional group in one molecule is an ester of acrylic acid, methacrylic acid, and a derivative of styrene. Examples of m=1 include methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxy Ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 1,4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate, glycidyl acrylate, glycidyl methacrylate, Examples include styrene, methylstyrene, chlorostyrene, bromostyrene, chloromethylstyrene, methoxystyrene, and the like.

Examples of m≧2 include ethylene glycol diacrylate, ethylene glycol dimethacrylate,
Diethylene glycol diacrylate, diethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, 2,2-bis(4-acryloxyethoxyphenyl)propane, 2,2-bis (4-
Methacryloxyethoxyphenyl)propane, 2.2-
Bis(4-acryloxyjethoxyphenyl)propane, 2,2-bis(4-methacryloxyjethoxyphenyl)propane, 2゜2-bis(4-acryloxyprobyloxyphenyl)propane, 2I 2-bis(4 -methacryloxyprobyloxyphenyl)propane, ], ]3
-butanediol cyacrylate 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1
．． 6-hexanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, spiroglycol diacrylate, spiroglycol dimethacrylate, epoxy Acrylate, epoxy methacrylate, 2-propenoic acid (2-[1,1-dimethyl-2-[(1-oxo-2-propenyl)oxy]ethyl]-5-ethyl-
1,3-dioxan-5-ylcomethyl ester, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacrylate) (royloxyethyl) hydroxyethyl isocyanurate, tris (acryloyloxyethyl) isocyanurate, tris (methacryloyloxyethyl) isocyanurate, pentaerythritor tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Hexamethacrylate, methyltri(acryloyloxyethoxy)silane,
Glycerol diacrylate, glycerol dimethacrylate, glycerol methacrylate acrylate, dibromneopentyl glycol diacrylate, dibromneopentyl glycol dimethacrylate, divinylbenzene, urethane acrylates, urethane methacrylates, 1,1,3,3.5.5 -hexa(acryloyloxy)cyclotriphosphoine, 1.1,3,3,
5.5-hexa(methacryloyloxy)cyclotriphosphoin, 1,1,3゜3.5.5-hexa(methacryloylethylenedioxy)cyclotriphosphoin, 1,
Examples include 1,3.3°5.5-hexa(methacryloylethylenedioxy)cyclotriphosphoine.

As a method for producing a transparent resin having high surface hardness according to the present invention, a monomer (A) represented by the following general formula (I) and (in the formula,
The definition of R is defined by ■■■■ described in (1) above. ) Copolymerization by combining a monomer (B) having m CH2=CH-C-0- groups and one type of functional group in one molecule so that (n0m) is an integer of 3 or more. It can be obtained by

Furthermore, for the purpose of viscosity adjustment, monomers having an isopropenylphenyl group other than the above monomer (A), such as diisopropenylbenzene, N-(3-isopropenyl-α, α
-dimethylbenzyl)-2-acryloyloxycarbamate, N-(3-isopropenyl-α,α-dimethylbenzyl)-2-methacryloyloxycarbamate, etc. may be added.

Furthermore, in this copolymerization, the ratio of the isopropenyl group to the CH2=CH-C-0- group in the mixture of the monomers is determined by the type of functional group possessed by the monomer and the structure of the monomer. Although it cannot be determined unconditionally based on factors such as, CH2-CH-C-0
It is preferable to carry out copolymerization in such a way that the sum total of the - groups and the groups is in the range of 0.5 to 10 equivalents.

This copolymerization is a radical copolymerization, and the polymerization method can be not only thermal polymerization but also a method using ultraviolet rays, gamma rays, etc., and it is also possible to perform not only a single method but also a combination of methods.

Radical polymerization initiators for thermal polymerization are not particularly limited, and include known benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxy carbonate, di-2-ethylhexyl peroxy carbonate, and t-butyl peroxy carbonate. Peroxides such as barreto and azo compounds such as azobisisobutyronitrile are used in proportions of 0.01 to 5% by weight.

The photosensitizer in the case of ultraviolet curing is not particularly limited, and may include known benzoyl compounds, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, 2-hydroxy-2-
Benzoylpropane, azobisisobutyronitrile, benzyl, thioxanthone, nphenyl disulfide, etc. are used in a proportion of 0.01 to 5% by weight.

When using radiation such as gamma rays, a polymerization initiator is generally not necessary.

Further, in the present invention, the method for obtaining a plate or lens using a highly hard transparent resin is not particularly limited, and any known manufacturing method can be employed. A typical manufacturing method is a cast polymerization method. For example, a radical initiator or photosensitizer is added to the monomer mixture of the above combination into a mold that combines a gasket or spacer and a glass or metal mold, and after thorough mixing and defoaming, the mixture is injected and heated. Or harden by irradiation with ultraviolet rays or radiation. Of course, additives such as ultraviolet absorbers, antioxidants, dyes, near-infrared absorbers, mold release agents, and antistatic agents can be added to the mixture before polymerization to the extent that they do not interfere with polymerization and curing.

Furthermore, when using the material in the form of a thin film, a known method for producing a thin film can be employed. That is, using roll coating, spray coating, flow coating, dipping, etc., a radical initiator or photosensitizer is added to the monomer mixture of the above combination, or a mixture thereof is diluted with a solvent, and then the resin, Coating to base materials such as metal and wood.

When a solvent is used, the solvent is volatilized and then cured by heating or irradiation with ultraviolet rays or radiation. At this time, additives such as ultraviolet absorbers, antioxidants, dyes, pigments, near-infrared absorbers, antistatic agents, inorganic compound fine particles, fillers, etc. are added to the mixture before polymerization to the extent that they do not interfere with polymerization and curing. can do.

The high-hardness transparent resin plate obtained in this way has excellent scratch resistance, and can also be made into a material with excellent chemical resistance, heat resistance, processability, etc., so it can be used as a glazing material and a protection material for display devices. Used for covers, etc. Further, by polymerizing the resin in a lens mold or processing the resin by cutting, polishing, etc., an optical lens having the same characteristics as described above can be obtained.

Furthermore, a thin film of highly hard and transparent resin on other resins, metals, wood, etc. is used as a covering material, ie, a hard coat material, with excellent scratch resistance, chemical resistance, etc.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the same extent by these Examples. Parts in the examples represent parts by weight.

First, a synthesis example of monomer (A) used in the present invention will be explained. Parts in the synthesis examples represent parts by weight.

(Synthesis Example 1) 13.4 parts of 3-isopropenylphenol, 11.1 parts of isophorone diisocyanate, 0.1 part of dibutyltin dilaurate, and 10 parts of toluene were mixed and the reaction solution temperature was adjusted to 70°C.
The reaction was carried out by stirring for 1 hour while maintaining the temperature. After the reaction was completed, the reaction solution was concentrated.

The concentrated liquid was purified by chromatography to obtain 22.3 parts of the following structural monomer in the form of a colorless and transparent liquid.

(Synthesis Example 2) 20.0 parts of 3-isopropenylphenol, 30 parts of ethanol, and 10 parts of a 50% aqueous sodium hydroxide solution are mixed and dissolved and refluxed. 12.7 parts of dibromoethane was added dropwise thereto, and after the addition was completed, the mixture was allowed to react under reflux for 8 hours. After the reaction was completed, the solvent was concentrated, toluene was added, and the mixture was washed with a 5% aqueous sodium hydroxide solution and water, dried, concentrated, and recrystallized to obtain 12.3 parts of a colorless crystalline monomer having the following structure.

(Synthesis Example 3) 13.4 m of 3-isopropenylphenol, 240 parts of water, and 4.8 parts of sodium hydroxide are mixed and dissolved. While vigorously stirring, a solution of 9.1 parts of adipic acid chloride in 200 parts of methylene chloride was added dropwise, and after the addition was completed, the mixture was reacted for 2 hours at room temperature and for 1 hour under refluxing methylene chloride. The methylene chloride layer was washed with 5% sodium hydroxide solution, dried, distilled off, and recrystallized from ethanol to obtain 14.0 parts of a white solid monomer having the structure shown below.

(Synthesis Example 4) 13.4 parts of 4-isopropenylphenol is dissolved in a mixed solution of 30 parts of ethanol, 5 parts of water, and 4.0 parts of sodium hydroxide, and heated to reflux.

17.0 parts of iodoethane was added dropwise thereto, and the mixture was allowed to react under reflux for 2 hours. After the reaction is completed, the solvent is distilled off and the formed precipitate is filtered off. The filtrate was distilled under reduced pressure to obtain 12.2 parts of a colorless transparent liquid monomer having the structure shown below.

(Synthesis Example 5) 13.4 parts of 3-isopropenylphenol, 10.0 parts of n-butyl isocyanate, 20 parts of chloroform, and 0.1 part of dibutyltin dilaurate were mixed, and the mixture was stirred for 1 hour under refluxing chloroform to react. I did it. After the reaction was completed, the reaction solution was concentrated.

The concentrated solution was purified by chromatography to obtain 20.5 parts of a colorless liquid monomer having the structure shown below.

2C (Synthesis Example 6) 13.4 parts of 4-isopropenylphenol, 5 parts of benzene
0 parts of triethylamine and 15.0 parts of triethylamine were mixed, 8.6 parts of acetic acid chloride was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 2 hours to react. After the reaction was completed, the reaction solution was filtered and concentrated. The concentrated solution was purified by chromatography to obtain 16.3 parts of a colorless liquid monomer having the structure shown below.

(Example 1) Monomer 122 with the following structure obtained in the same manner as Synthesis Example 1
．． 7 parts, pentaerythritol tetraacrylate 8
After adding 8.1 parts of benzoyl peroxide and mixing well, add 2.4 parts of benzoyl peroxide, mix, defoamer, and apply this liquid to a 5 mm thick polyvinyl chloride plate around two 5 mm thick glass plates. Place a spacer in the mold and tighten it firmly with a clamp.
The temperature was raised to 0° C. over 1.5 hours to perform polymerization, and then cooled and released from the mold to obtain a transparent resin plate with a smooth surface. The pencil hardness of this board (according to the JIS-5400 method) is 7H, and the chemical resistance is good (if it does not leave a pencil HB residue after being immersed in isopropanol and toluene for 24 hours at room temperature, it is considered good). It also has good heat resistance (after leaving it in a hot air dryer at 120°C for 4 hours, the polymer is taken out and no changes such as coloration or surface distortion are observed with the naked eye). It was possible to cut it with a saw, and it was also possible to grind it with a beading machine for processing eyeglass lenses.

(Example 2) Monomer 70 having the following structure obtained in the same manner as Synthesis Example 3.
Add 37.6 parts of divinylbenzene to 2 parts and mix well, then add 1.0 part of benzoyl peroxide and mix.
After degassing, this liquid was placed in a 5 mm thick polyvinyl chloride spacer around two 51 thick glass plates.
The mixture was poured into a mold that was tightly tightened with a clamp, and the temperature was raised from 70°C to 140°C over 1.5 hours in a polymerization hot air oven for polymerization. After that, it was cooled and released from the mold. A transparent resin plate with a smooth surface was obtained. This board had a pencil hardness of 5H, had good chemical resistance and heat resistance, could be cut with a metal saw, and could be ground with a beading machine for processing eyeglass lenses.

(Example 3) Monomer 81 of the following structure obtained in the same manner as Synthesis Example 4
．． After adding 88.1 parts of pentaerythritol tetraacrylate to 1 part and mixing well, 0.0 parts of benzoyl peroxide was added.
Add 9 parts, mix, defoamer, and pour this liquid into two 5 m
A spacer made of polyvinyl chloride with a thickness of 5 m is placed around the glass plate, poured into a mold tightly tightened with a clamp, and heated at 70 to 140 °C in a hot air oven for polymerization.
After polymerization was carried out by raising the temperature over 1.5 hours, the mixture was cooled and released from the mold to obtain a transparent resin plate with a smooth surface. This board had a pencil hardness of 7H, had good chemical resistance and heat resistance, could be cut with a metal saw, and could be ground with a beading machine for processing eyeglass lenses.

(Example 4) 0.1 part of benzoyl peroxide was added to 30 parts of the monomer mixture prepared in the same manner as in Example 1, and the pore size was adjusted to 5 μm under pressure.
Filtered through a filter, poured into a +2 diopter lens mold for diethylene glycol diallyl carbonate, heated from 70°C to 140°C over 3 hours to polymerize, cooled, released from the mold, and the surface was removed. A smooth and transparent convex lens was obtained. The surface pencil hardness is 7H,
The refractive index measured by an Atsube refractometer was 1.53.

(Example 5) 0.2 parts of benzoyl peroxide was added to 20.0 parts of the monomer mixture prepared in the same manner as in Example 2, mixed well, defoamed, and coated on a steel plate with a coating bar to a thickness of 50 μm.
It was coated and cured by heating at a temperature of 140° C. for 30 minutes to obtain a transparent thin film with a smooth surface. The pencil hardness of the paint film is 7
H, substrate test (JIs-54 (according to 10)) is good, heat resistance (good if no abnormality was observed after being left in a hot air drying mold at 120°C for 10 hours) was also good.

(Comparative Example 1) 3.0 parts of benzoyl peroxide was added to 100 parts of diethylene glycol diallyl carbonate, mixed and defoamed, and this liquid was spread around two 5 mm thick glass plates for 5.0 parts.
After inserting a spacer made of polyvinyl chloride with a thickness of 100 yen and tightening it firmly with a clamp, it was poured into the mold and polymerized by heating from 50°C to 120°C for 3 hours in a hot air oven for polymerization. During the process, rapid polymerization occurred at around 70°C, and the polymer was peeled off from the glass mold and colored yellow.

By heating and polymerizing the resin from 50°C to 120°C over 10 hours, it was possible to obtain a resin plate without peeling for the first time, but the pencil hardness of the resin obtained was 3H.

(Comparative Example 2) Add 18.8 parts of m-xylylene diisocyanate to 20.0 parts of methyl methacrylate, further add 0.5 parts of dibutyltin dilaurate, and heat until the internal temperature reaches 60°C. .0
A viscous urethane compound methyl methacrylate mixture in which the absorption of the isocyanate group almost disappeared in the infrared absorption spectrum was obtained by gradually adding 50% of the mixture. Add 0.3 parts of benzoyl peroxide to this, mix and defoam, then insert a 5mm thick vinyl chloride spacer around two 5+nn+ thick glass plates and tighten firmly with a clamp. The mixture was poured into a mold and heated and polymerized in a hot air oven for polymerization from 45°C to 120°C over 3 hours.
Rapid polymerization occurred at around 65°C, and the polymer peeled off from the glass mold.

(Comparative Example 3) 0.5 parts of benzoyl peroxide was added to 50 parts of trimethylolpropane triacrylate, mixed and defoamed, and this liquid was spread around two 5 mm thick glass plates for 50 parts.
A mm-thick polyvinyl chloride spacer was inserted, the mixture was poured into a mold that was tightly tightened with a clamp, and the temperature was raised from 60°C to 140°C over 3 hours in a hot air oven for polymerization. Rapid polymerization soon occurred and the polymer peeled off from the glass mold.

〔Effect of the invention〕

The resin of the present invention can be extremely easily controlled during the polymerization process, and therefore has extremely good moldability without causing peeling, whitening, or cracking during molding polymerization, and can be molded with high precision. Furthermore, the resin of the present invention has high surface hardness and excellent transparency.

Furthermore, the resin of the present invention can be made to have excellent chemical resistance and heat resistance, and in combination with high surface hardness, it also has excellent processability such as cutting and machining.

Therefore, it can be suitably used for glazing materials, protective covers for display devices, optical lenses, hard coat materials, etc.

Claims (1)

[Claims] (1) Monomer (A) represented by the following general formula (I), ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is [1] isopropenyl There are ▼ mathematical formulas, chemical formulas, tables, etc. bonded to phenoxy groups ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼Aliphatic residues with or without functional groups chosen from the group ▲Formula,
There are chemical formulas, tables, etc. ▼ indicates isopropenylphenoxy group and is not included in R) or [2] There are ▲ mathematical formulas, chemical formulas, tables, etc. bonded to isopropenyl phenoxy group ▼ group, ▲ mathematical formula, chemical formula, There are tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ alicyclic residues with or without functional groups selected from groups ▲ mathematical formulas, chemical formulas , tables, etc. ▼ indicates isopropenylphenoxy group and is not included in R) or [3] There are ▲ mathematical formulas, chemical formulas, tables, etc. bonded to isopropenyl phenoxy group ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. There are ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. an aliphatic residue having at least one member selected from the group consisting of a ring, an aromatic ring, and a heteroatom ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ indicates an isopropenyl phenoxy group and is not included in R) or , [4] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a group,
n represents an integer from 1 to 4. ) One molecule contains at least one functional group selected from ▲ has a mathematical formula, chemical formula, table, etc. ▼ group, ▲ has a mathematical formula, chemical formula, table, etc. ▼ group, or ▲ has a mathematical formula, chemical formula, table, etc. ▼ group Monomer (B) having m groups and (n
A high-hardness transparent resin made of crosslinked polymers that are copolymerized in combination such that +m) is an integer of 3 or more. (2) High hardness and transparency made of a crosslinked polymer containing a structural unit represented by the following general formula (II) and/or (III) made of monomer (A) and monomer (B) according to claim 1. resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is bonded to the [1] isopropenylphenoxy group. There are chemical formulas, tables, etc. ▼ groups, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ aliphatic residues with or without functional groups selected from the groups ▲ mathematical formulas,
There are chemical formulas, tables, etc. ▼ indicates isopropenylphenoxy group (not included in R) or [2] There are ▲ mathematical formulas, chemical formulas, tables, etc. bonded to isopropenyl phenoxy group ▼ group, ▲ mathematical formula, chemical formula, There are tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ alicyclic residues with or without functional groups selected from groups ▲ mathematical formulas, chemical formulas , tables, etc. ▼ indicates an isopropenylphenoxy group and is not included in R) or [3] There are ▲ mathematical formulas, chemical formulas, tables, etc. bonded to the isopropenyl phenoxy group ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. There are ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. An aliphatic residue having at least one type selected from the group consisting of a ring, an aromatic ring, and a hetero atom (nitrogen atom, sulfur atom, oxygen atom, etc.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is an isopropenylphenoxy group. (not included in R) or [4]-C- group, R' is hydrogen or methyl group, Y is ▲ mathematical formula, chemical formula, table, etc. ▼... group, ▲ mathematical formula, chemical formula, There are tables, etc. ▼...Groups, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼...Groups, n
(n+m) represents an integer of 1 to 4, and (n+m) represents an integer of 3 or more. (3) A glazing material made of the highly hard transparent resin according to claim 1. (4) A protective cover for a display device made of the highly hard transparent resin according to claim 1. (5) An optical lens made of the highly hard transparent resin according to claim 1. (6) A hard coat material comprising the highly hard transparent resin according to claim 1. (7) General formula (IV) (V) (VI) (VII) (VIII) below
Monomer (A), which is at least one type selected from the group consisting of monomers represented by (IX), and ▲ mathematical formula, chemical formula, table, etc. in one molecule ▼ group, ▲ mathematical formula, chemical formula, table, etc. A monomer (B) having m functional groups of at least one kind selected from ▼ groups, or ▲ mathematical formulas, chemical formulas, tables, etc. groups, and (n + m)
A high-hardness transparent resin made of crosslinked polymers that are copolymerized by combining them so that they become an integer of 3 or more. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, n=1, R is -CH_3, -C_2H_5, -C
_3H_7, -C_4H_9, -C_5H_1_1, -
C_6H_1_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
represents. Further, the positions of the substituents on the aromatic ring represent the o-, m-, and p-positions. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, n=1, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Further, the positions of the substituents on the aromatic ring represent the o-, m-, and p-positions. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) (In the formula, n = 1, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, % expression, and . Further, the positions of the substituents on the aromatic ring represent the o-, m-, and p-positions. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) (In the formula, n=2, R is -(CH_2)_2-, -(CH_
2)_3-, -(CH_2)_4-, -(CH_2)_
5-, -(CH_2)_6-. Further, the positions of the substituents on the aromatic ring represent the o-, m-, and p-positions. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VIII) (In the formula, n = 2, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas , tables, etc. Represents ▼. Also, the positions of substituents on the aromatic ring represent the o, m, and p-positions.) ▲ Formula,
There are chemical formulas, tables, etc. ▼ (IX) (in the formula, n = 2, R is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, tables, etc. There are▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Represents. Further, the positions of the substituents on the aromatic ring represent the o-, m-, and p-positions. )