JPH04266927A - Transparent resin having high hardness - Google Patents

Abstract

PURPOSE:To obtain the title resin by readily controllable polymerization useful for glazing material, optical lens, etc., excellent chemical resistance, processability, impact resistance, etc., by copolymerizing a specific functional group-containing monomer with a monomer containing two or more SHs in one molecule. CONSTITUTION:For example, (A) a monomer (e.g. N-(3-isopropenyl-alpha,alpha- dimethylbenzyl)-2-acryloyloxyethylcarbamate) containing functional groups shown by formula I (X is O or S), formula II (R is H or methyl) and formula II is radical-copolymerized with (B) a monomer (e.g. methanedithiol) containing two or more SHs in one molecule to give the objective resin.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention has high surface hardness,
The present invention relates to a transparent resin that has excellent scratch resistance, heat resistance, chemical resistance, and impact resistance, as well as glazing materials, protective covers for display devices, and optical lenses made of the resin.

0002

[Prior Art] Conventionally, methacrylic resin, polycarbonate resin, polystyrene resin, etc. have excellent transparency, impact resistance, processability, mass productivity, etc., and have been used for windows of vehicles, residences, schools, sports facilities, etc. As a glazing material for veranda wainscoting, balconies, etc., various instrument panels,
It is used as a protective cover for display devices such as computer displays, LCD televisions, and vending machine front panels, as well as for optical lenses, lighting covers, signboards, safety glasses, and optical disc substrates. When applied to these applications, in particular glazing materials, protective covers for display devices, and optical lenses, their transparency, optical properties, mechanical strength, and rigidity, as well as their visibility, aesthetics, and durability are important. Scratch resistance, that is, high surface hardness, chemical resistance, heat resistance, and impact resistance are required from the viewpoint of safety. However, since these general-purpose transparent resins have a linear polymer structure,
Surface hardness, chemical resistance, heat resistance, etc. are not sufficient, and even when these resins are hard coated to improve surface hardness and chemical resistance, they still do not always have sufficient performance. I can't say that it is. In order to solve these problems, diethylene glycol diallyl carbonate resin and urethane polyacrylic ester
Transparent resins made of polymers having a crosslinked structure have been proposed, such as Japanese Patent Application Laid-open No. 3610 and Japanese Patent Application Laid-open No. 63-75022. We proposed a resin that further increases productivity and improves productivity. (Unexamined Japanese Patent Publication No. 2-84406)

0
003]

[Problems to be Solved by the Invention] However, although the above-mentioned transparent resin proposed by us has easy polymerization control, high surface hardness, and excellent chemical resistance and heat resistance, it has poor impact resistance. The problem was that there was a shortage. Therefore, an object of the present invention is to provide a transparent resin with improved impact resistance while maintaining as much as possible the properties of easy polymerization control, high surface hardness, and excellent chemical resistance and heat resistance. That's true.

0004

[Means for Solving the Problems] The present inventors have conducted extensive research in order to solve the above problems. As a result, by copolymerizing a monomer having two or more -SH groups in one molecule, a relatively flexible crosslinking bond in which -SH groups are added to an unsaturated bond can be created. The present invention was completed based on the discovery that impact resistance is improved compared to transparent resins. That is, the present invention provides: (1) In one molecule, the following general formula (I) (Chemical formula 6)

000
5]

[Image Omitted] A functional group represented by [Image Omitted] and the following general formula (II) or (II
I) (Chem. 7)

[0006]

Impact resistance obtained by copolymerizing a monomer (A) having a functional group represented by [Chemical formula 7] and a monomer (B) having two or more -SH groups in one molecule. High hardness transparent resin with improved properties (
2) The above monomer (A) and monomer (B), and the following group (chemical formula 8)

[0007]

A monomer having at least one functional group selected from [Image Omitted]
C) High hardness transparent resin with improved impact resistance obtained by copolymerizing with (3) the following general formula (IV) (Chemical formula 9)

[0008]

[Formula 9] (wherein, group residue or heterocyclic residue, n represents an integer from 1 to 4, when n = 1, X is an oxygen atom or a sulfur atom, and when n≧2, X is an oxygen atom or a sulfur atom. a monomer (D) represented by 1 or 1 or 2 oxygen atoms and the rest sulfur atoms, or 1 sulfur atom and the rest oxygen atoms;
A monomer (E) having m at least one kind of functional group selected from the group of groups represented by (Chemical formula 8) in the molecule is combined such that (n+m) is an integer of 3 or more, and Body (B
The present invention relates to high-hardness transparent resins with improved impact resistance obtained by copolymerizing them with the addition of the following compounds, as well as glazing materials, protective covers for display devices, and optical lenses made of these resins.

The monomer (A) used in the present invention has a functional group represented by the general formula (I) (Chemical formula 6) and a functional group represented by the general formula (II) or (III) (Chemical formula 7) in one molecule. It is a monomer that has both the expressed functional groups, isopropenyl-α, α
- Dimethylbenzylisocyanate and a compound (compound F ) is a carbamate or thiocarbamate obtained by reacting with Specifically, 3-isopropenyl-α,α-dimethylbenzyl isocyanate or 4-isopropenyl-α,α-dimethylbenzyl isocyanate is used as isopropenyl-α,α-dimethylbenzyl isocyanate. Also, compound F
Examples include compounds obtained by ring-opening an epoxy group or thiirane group with acrylic acid or methacrylic acid, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 1,4-butylene glycol monomethacrylate, 1,4-butylene glycol monoacrylate, glycerol-1,2-diacrylate, glycerol-1,2-dimethacrylate, glycerol-1,3-diacrylate, glycerol-
1,3-dimethacrylate, glycerol-1-acrylate-3-methacrylate, acrylic acid or methacrylic acid ring-opening reaction product of phenyl glycidyl ethers, 3
-phenoxy-2-hydroxypropyl acrylate,
3-phenoxy-2-hydroxypropyl methacrylate, 2,4-dibromophenoxy-2-hydroxypropyl acrylate, 2,4-dibromophenoxy-2-
Hydroxypropyl methacrylate, bisphenol A
Acrylic acid or methacrylic acid ring-opening reaction product of diglycidyl ether, pentaerythritol triacrylate,
Pentaerythritol trimethacrylate, vinylbenzyl alcohol, vinylthiobenzyl alcohol, bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, etc. are used.

[0010] In order to obtain a carbamate ester or thiocarbamate ester using these, the isocyanate group of isopropenyl-α,α-dimethylbenzyl isocyanate is reacted with a hydroxyl group or a mercapto group, but at this time, the synthesis reaction To facilitate the process, a tin compound such as dibutyltin dilaurate or dimethyltin chloride or an amine such as morpholine or dimethylaminobenzene may be added, but in order to prevent coloring due to the subsequent radical reaction, a tin compound should be selected. It is preferable. In addition, when a solvent is used, the solvent is distilled off after the synthesis reaction, and the monomer (A) is prepared for the next radical polymerization without purification or purification.

Specifically, the monomer (A) is N-(
3-isopropenyl-α,α-dimethylbenzyl)-2
-acryloyloxyethyl carbamate, N-(3-
Isopropenyl-α,α-dimethylbenzyl)-2-methacryloyloxyethylcarbamate, N-(4-isopropenyl-α,α-dimethylbenzyl)-2-acryloyloxyethylcarbamate, N-(4-isopropenyl-α , α-dimethylbenzyl)-2-methacryloyloxyethylcarbamate, N-(3-isopropenyl-α,α-dimethylbenzyl)-1-acryloyloxypropan-2-ylcarbamate, N-(3-
isopropenyl-α,α-dimethylbenzyl)-1-methacryloyloxypropan-2-ylcarbamate,
N-(4-isopropenyl-α,α-dimethylbenzyl)-1-acryloyloxypropan-2-ylcarbamate, N-(3-isopropenyl-α,α-dimethylbenzyl-1,3-diacryloyloxypropane -2
-ylcarbamate, N-(3-isopropenyl-α,
α-dimethylbenzyl)-1,3-dimethacryloyloxypropan-2-ylcarbamate, N-(3-isopropenyl-α,α-dimethylbenzyl)-1-acryloyloxy-3-methacryloyloxypropane-2
-ylcarbamate, N-(4-isopropenyl-α,
α-dimethylbenzyl)-1,3-diacryloyloxypropan-2-ylcarbamate, N-(3-isopropenyl-α,α-dimethylbenzyl)-2,2-diacryloyloxymethyl-3-acryloyloxypropyl Carbamate, N-(4-isopropenyl-α,α
-dimethylbenzyl)-2,2-dimethacryloyloxymethyl-3-methacryloyloxypropylcarbamate and the like. When the isocyanate compound is reacted with a mercapto group, the above carbamate becomes a thiocarbamate.

The monomer (B) having two or more -SH groups in one molecule used in the present invention includes, for example, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2 -propanedithiol, 1,3-
Propanedithiol, 2,2-propanedithiol,
1,6-hexanedithiol, 1,2,3-propane trithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane - 1,2-dithiol, 2-methylcyclohexane- 2,3-dithiol, bicyclo[2
,2,1]Pepta-exo-cis-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid bis(2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2- mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-
Dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercapto Propyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-
mercaptoacetate), ethylene glycol bis(3
-mercaptopropionate), trimethylolpropane bis(2-mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate) aliphatic polythiols such as

001
3] 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene,
1,2-bis(mercaptomethyl)benzene, 1,3
-bis(mercaptomethyl)benzene, 1,4-bis(
mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)
Benzene, 1,2-bis(mercaptomethyleneoxy)benzene, 1,3-bis(mercaptomethyleneoxy)benzene, 1,4-bis(mercaptomethyleneoxy)benzene, 1,2-bis(mercaptoethyleneoxy)benzene, 1,3-bis(mercaptoethyleneoxy)benzene, 1,4-bis(mercaptoethyleneoxy)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene, 1,2,3-
Tris(mercaptomethyl)benzene, 1,2,4-
Tris(mercaptomethyl)benzene, 1,3,5-
Tris(mercaptomethyl)benzene, 1,2,3-
Tris(mercaptoethyl)benzene, 1,2,4-
Tris(mercaptoethyl)benzene, 1,3,5-
Tris(mercaptoethyl)benzene, 1,2,3-
Tris(mercaptomethyleneoxy)benzene, 1,
2,4-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptomethyleneoxy)
Benzene, 1,2,3-tris(mercaptoethyleneoxy)benzene, 1,2,4-tris(mercaptoethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 1,2,3, 4
-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,4, 5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-
Tetrakis(mercaptoethyl)benzene, 1,2,
3,5-tetrakis(mercaptoethyl)benzene,
1,2,4,5-tetrakis(mercaptoethyl)benzene, 1,2,3,4-tetrakis(mercaptomethyleneoxy)benzene, 1,2,3,5-tetrakis(mercaptomethyleneoxy)benzene, 1,2 ,4
, 5-tetrakis(mercaptomethyleneoxy)benzene, 1,2,3,4-tetrakis(mercaptoethyleneoxy)benzene, 1,2,3,5-tetrakis(
Mercaptoethyleneoxy)benzene, 1,2,4,5
-tetrakis(mercaptoethyleneoxy)benzene,
2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1 ,5
-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedi Methanethiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,
3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di(p
Aromatic polythiols such as -mercaptophenyl)pentane, 2-methylamino-4,6-dithiol-sy
m-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4,6-
dithiol-sym-triazine, 2-morpholino-
4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym
-triazine, 2-methoxy- 4,6-dithiol-
sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine,
2-thiobutyloxy-4,6-dithiol-sy
polythiol containing a heterocycle such as m-triazine,

1,2-bis(mercaptomethylthio)benzene, 1,3-bis(mercaptomethylthio)benzene, 1,4-bis(mercaptomethylthio)benzene, 1,2-bis(mercaptoethylthio)benzene, 1, 3-bis(mercaptoethylthio)benzene,
1,4-bis(mercaptoethylthio)benzene,
1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio) ) benzene, 1,2,4-tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, 1,2,3,4-tetrakis(mercaptomethylthio)benzene, 1,2, 3,5-tetrakis(mercaptomethylthio)benzene, 1,2
,4,5-tetrakis(mercaptomethylthio)benzene, 1,2,3,4-tetrakis(mercaptoethylthio)benzene, 1,2,3,5-tetrakis(mercaptoethylthio)benzene, 1,2,4, 5-tetrakis(mercaptoethylthio)benzene, etc., and aromatic polythiols containing a sulfur atom in addition to the mercapto group such as nuclear alkylated products thereof, bis(mercaptomethyl) sulfide, bis(mercaptoethyl) sulfide,
Bis(mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis (2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropyl)ethane,
1,3-bis(mercaptomethylthio)propane, 1
, 3-bis(2-mercaptoethylthio)propane,
1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris (3-mercaptopropylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide , 2,5-dimercapto-1,4-dithiane, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) disulfide, etc., and esters of thioglycolic acid and mercaptopropionic acid thereof,

Hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate) , hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate),
Hydroxymethyl disulfide bis(3-mercaptopropionate), Hydroxyethyl disulfide bis(
2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis( 2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(2
-mercaptoacetate), 1,4-dithiane-2
,5-diolbis(3-mercaptopropionate)
, thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionate bis(2-mercaptoethyl ester), 4,4-thiodibutyric acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester) mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 4,4
-Dithiodibutyrate bis(2-mercaptoethyl ester), thiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionate bis(2,
3-dimercaptopropyl ester), dithioglycolic acid bis(2,3-dimercaptopropyl ester)
, aliphatic polythiol containing a sulfur atom in addition to the mercapto group such as dithiodipropionic acid bis(2,3-dimercaptopropyl ester), 3,4-thiophenedithiol, 2,5-dimercapto-1,3,4- Examples include heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as thiadiazole.

The monomer (C) used in the present invention is (chemical formula 8).
) is a monomer having at least one kind of functional group selected from the group of groups, and is an ester of acrylic acid, methacrylic acid, and a derivative of styrene. For example, 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, ethoxyethyl 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, styrene, methylstyrene, chlorostyrene, bromostyrene, chloromethylstyrene, methoxystyrene, 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 - screw (4
-acryloxydiethoxyphenyl)propane, 2,2-
Bis(4-methacryloxydiethoxyphenyl)propane, 2,2-bis(4-acryloxypropyloxyphenyl)propane, 2,2-bis(4-methacryloxypropyloxyphenyl)propane, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,
4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, spiroglycol diacrylate acrylate, 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-yl] methyl ester, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl) Hydroxyethyl isocyanurate, tris(acryloyloxyethyl) isocyanurate, tris(methacryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methyl tri(acrylate) (royloxyethoxy) silane, glycerol diacrylate, glycerol dimethacrylate, dibromneopentyl glycol diacrylate, dibromneopentyl glycol dimethacrylate, divinylbenzene, urethane acrylates, urethane methacrylates, 1,1,3,3,5 ,5-hexa(acryloyloxy)cyclotriphosphozene, 1,1,3,
3,5,5-hexa(methacryloyloxy)cyclotriphosphozene, 1,1,3,3,5,5-hexa(acryloylethylenedioxy)cyclotriphosphozene,
Examples include 1,1,3,3,5,5-hexa(methacryloylethylenedioxy)cyclotriphosphozene. The monomer (D) used in the present invention is represented by the general formula (IV)
(Chem.10)

[0017]

[Formula 10] (wherein, group residue or heterocyclic residue, n represents an integer from 1 to 4, when n = 1, X is an oxygen atom or a sulfur atom, and when n≧2, X is an oxygen atom or a sulfur atom. atoms or one or two
(one is an oxygen atom and the other is a sulfur atom, or one is a sulfur atom and the rest is an oxygen atom), specifically, isopropenyl-α,α-dimethylbenzyl isocyanate and a halogen atom in the residue. , oxygen atom, alicyclic ring,
Aliphatic residues, alicyclic residues or heterocyclic residues with or without a heterocyclic or aromatic ring, and compounds having 1 to 4 -OH or -SH groups are referred to as isopropenyl-α,α-
A carbamate ester or a carbamate thioester compound obtained by reacting an isocyanate group of dimethylbenzyl isocyanate with an -OH group or a -SH group is exemplified. Here, in general formula (IV), when n is 2 or more, X is a compound in which all oxygen atoms or sulfur atoms are present, or one or two are oxygen atoms and the rest are sulfur atoms, or one is a sulfur atom and the rest is oxygen atoms. Also included are compounds that are atoms. Furthermore, although it depends on the steric rigidity of the structure of the residue -R, in general, the lower the molecular weight, the more preferable it is, and the molecular weight of the residue part is particularly preferably 15 to 500.

Aliphatic residues, alicyclic residues with or without a halogen atom, oxygen atom, alicyclic ring, heterocycle or aromatic ring in the residue used in the above method for producing monomer (D) Compounds having 1 to 4 group residues or heterocyclic residues and -OH groups or -SH groups include, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, cyclopentanol, cyclo hexanol, cycloheptanol,
Cyclooctanol, 2,2,2-trichloroethanol, 2,2,2-trifluoroethanol, 1,3-dichloro-2-propanol, 2,3-dichloro-1-propanol, 2,3-dibromo-1- Propanol, 1
-Chloro-2-propanol, 3-chloro-1-propanol, 2-chloroethanol, 2-bromoethanol, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, cyclohexane Thiol, benzyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 2,5-hexanediol, diethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, dipropylene glycol, triethylene glycol, 1,2- Butanediol, 2-ethyl-1
, 3-hexanediol, spiroglycol, 1,4-
Cyclohexanediol, tricyclo[5,2,1,0
2,6 ] Decane-4,8-dimethanol, 3-chloro-1,2-propanediol, 3-bromo-1,2-propanediol, 2,3-dibromo-1,4-butanediol, dibromoneo Pentyl glycol, bisphenol A (2-hydroxyethyl) ether, bisphenol F (2-hydroxyethyl) ether, bisphenol S (2-hydroxyethyl) ether, bisphenol (2-hydroxyethyl) ether, tetrabromobisphenol A (2-hydroxy) ethyl) ether,
Benzenedimethanol, ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol, propanetrithiol, cyclohexanedithiol, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), bis( Mercaptomethyl)benzene, 2-hydroxyethyl disulfide, 2-mercaptoethanol, 1-mercapto-2-propanol, glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,
6-hexanetriol, 1,3,5-tris(2-hydroxyethyl)cyanuric acid, pentaerythritol,
Thretol, 3-mercapto-1,2-propanediol, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3
-mercaptopropionate), etc.

To obtain a carbamate ester compound or thiocarbamate ester compound using these,
It is based on the reaction between the isocyanate group of isopropenyl-α,α-dimethylbenzyl isocyanate and the -OH group or -SH group, but at this time, in order to facilitate the synthesis reaction,
Tin compounds such as dibutyltin dilaurate and dimethyltin dichloride, or amines such as morpholine and dimethylaminobenzene may be added as catalysts, but in order to prevent coloration due to the subsequent radical reaction, it is recommended to select a tin compound. preferable. Moreover, when a solvent is used, the solvent is distilled off after the synthesis reaction. Further, if necessary, the monomer (D) is purified and prepared for the next radical polymerization. Specifically, as the monomer (D), the following compounds (Formula 11), (Formula 12), (Formula 13), (Formula 14)
) etc.

[0020]

[Chemical formula 11]

[0021]

[Chemical formula 12]

[0022]

[Chemical formula 13]

[0023]

[Chemical Formula 14] The monomer (E) used in the present invention is a monomer having m at least one functional group selected from the group of (Chemical Formula 8), and includes acrylic acid and methacrylic acid. Derivatives of esters and 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, methoxy Ethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl 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, 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, and dipropylene glycol diacrylate. methacrylate, 2,2-bis(
4-acryloxyethoxyphenyl)propane, 2,2
-bis(4-methacryloxydiethoxyphenyl)propane, 2,2-bis(4-acryloxydiethoxyphenyl)propane, 2,2-bis(4-methacryloxydiethoxyphenyl)propane, 2,2-bis(4-methacryloxydiethoxyphenyl)propane, 4-Acryloxypropyloxyphenyl)propane, 2,2-bis(4-methacryloxypropyloxyphenyl)propane, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol Diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1
, 6-hexanediol dimethacrylate, 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-yl]methyl ester, trimethylolpropane triacrylate,
Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, bis(acryloyloxyethyl)
Hydroxyethyl isocyanurate, bis(methacryloyloxyethyl) hydroxyethyl isocyanurate,
Tris (acryloyloxyethyl) isocyanurate,
Tris(methacryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methyltri(acryloyloxyethoxy)silane, glycerol diacrylate, glycerol dimethacrylate, di Bromneopentyl glycol diacrylate, dibromneopentyl glycol dimethacrylate, divinylbenzene, urethane acrylates, urethane methacrylates, 1,1,3,3
, 5,5-hexa(acryloyloxy)cyclotriphosphozene, 1,1,3,3,5,5-hexa(methacryloyloxy)cyclotriphosphozene, 1,1,3,3
, 5,5-hexa(acryloylethylenedioxy)cyclotriphosphozene, 1,1,3,3,5,5-hexa(methacryloylethylenedioxy)cyclotriphosphozene, and the like.

The high hardness transparent resin of the present invention comprises monomer (A) and monomer (B), monomer (A), monomer (B) and monomer obtained by the above method. (C), or by copolymerizing monomer (D), monomer (B), and monomer (E). Furthermore, for purposes such as viscosity adjustment, a monomer having an isopropenylphenyl group other than the monomer (A) or monomer (D), such as diisopropenylbenzene, may be added. In addition, in the copolymerization of the present invention, an isopropenylphenyl group in the polymerization system in the mixture of the above monomers, a -SH group and the following group (Chemical formula 15)

[0026]

[Chemical Formula 15] Although the ratio cannot be determined unconditionally depending on the type of functional group possessed by the above-mentioned monomer and the structure of the monomer, a small proportion of -SH groups can sufficiently improve impact resistance. If the amount is too high, the polymer becomes rubbery and the surface hardness and rigidity are significantly reduced. Furthermore, if the proportion of the group represented by (Chemical Formula 15) is small, a polymer cannot be obtained, and if it is too large, it becomes difficult to control the polymerization. The ratio of -SH group used during copolymerization is usually 0.1 to 5 per equivalent of isopropenylphenyl group.
equivalent, preferably 0.3 to 1.5 equivalents, and the total sum of the groups of (Chemical formula 15) is usually in the range of 0.3 to 10 equivalents, preferably 0.5 to 6 equivalents.

The copolymerization in the present invention is radical copolymerization, and the polymerization method is not only thermal polymerization, but also methods using ultraviolet rays, gamma rays, etc.
It is also possible to do it in combination. Radical polymerization initiators used in thermal polymerization are not particularly limited, and include known benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2
Peroxides such as -ethylhexyl peroxycarbonate and t-butylperoxypivalate and azo compounds such as azobisisobutyronitrile can be used, and the amount used is from 0.01 to 5% by weight. The photosensitizer used in the case of ultraviolet curing is not particularly limited, and may include known benzoyl compounds, benzoyl methyl ether, benzoylethyl ether, benzoyl propyl ether, benzoin isobutyl ether, 2-hydroxy-2-benzoylpropane, azobisisobutyro Nitrile, benzyl, thioxanthone, diphenyl disulfide, etc. can be used.
The amount used is 0.01 to 5% by weight. When using radiation such as gamma rays, a polymerization initiator is generally not necessary.

Further, the method for obtaining a plate or lens using the highly hard transparent resin of the present invention is not particularly limited, and any known manufacturing method may 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, the mixture is thoroughly mixed, and the defoamed liquid is poured into a mold that combines a gasket or spacer and a glass or metal mold. Then, it is cured by heating or 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.

The high-hardness transparent resin plate of the present invention thus obtained has excellent scratch resistance, chemical resistance, heat resistance, impact resistance, workability, etc., and is suitable for use as glazing materials and protective covers for display devices. used. 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.

[0030]

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way. Example 1 To 201 parts of 3-isopropenyl-α,α-dimethylbenzyl isocyanate, 0.0 parts of dibutyltin dilaurate was added.
Add 5 parts and heat until the internal temperature reaches 60℃.
130 parts of hydroxyethyl methacrylate was gradually added to carry out a urethanization reaction, and a monomer with the following structure (chemical formula 16
) was obtained.

[0031]

[Chemical formula 16] To this, add 30 parts of ethylene glycol bis(3-mercaptopropionate), and further add 1.8 parts of t-butylperoxy-2-ethylhexanoate, mix well, and defoam. It was made into a homogeneous liquid. This liquid was poured into a mold with a 5 mm thick polyvinyl chloride spacer placed around two glass plates and tightly tightened with a clamp, and heated to 70°C to 150°C in a hot air oven for polymerization. 2
The temperature was raised over time to carry out polymerization. Thereafter, it was cooled and released from the mold to obtain a transparent resin plate with a smooth surface. Example 2 To 201 parts of 4-isopropenyl-α,α-dimethylbenzyl isocyanate, 0.0 parts of dibutyltin dilaurate was added.
Add 5 parts and heat until the internal temperature reaches 60℃.
214 parts of glycerol-1-acrylate-3-methacrylate was gradually added to carry out a urethanization reaction to obtain a monomer (chemical formula 17) having the following structure.

[0032]

[Chemical formula 17] To this, 19 parts of 1.6-hexanedithiol was added, and further, 2.1 parts of t-butylperoxy-2-ethylhexanoate was added to this, and the mixture was thoroughly mixed and defoamed to form a homogeneous liquid. . This solution was poured into a mold with a 5 mm thick polyvinyl chloride spacer placed around two glass plates and tightly tightened with a clamp, and placed in a hot air oven for polymerization at 70°C.
The temperature was raised from 150° C. to 150° C. over 2 hours to carry out polymerization. Thereafter, it was cooled and released from the mold to obtain a transparent resin plate with a smooth surface. Example 3 To 201 parts of 3-isopropenyl-α,α-dimethylbenzyl isocyanate, 0.0 parts of dibutyltin dilaurate was added.
Add 5 parts and heat until the internal temperature reaches 60℃.
116 parts of hydroxyethyl acrylate was gradually added to carry out a urethanization reaction, and a monomer of the following structural formula (Chemical formula 18
) was obtained.

[0033]

embedded image To this were added 61 parts of pentaerythritol tetrakis(3-mercaptopropionate), 141 parts of tris(acryloxethyl) isocyanurate, and 52 parts of styrene, and further to this was added t-butylperoxy-2- 2.8 parts of ethylhexanoate was added, mixed well, and defoamed to obtain a homogeneous liquid. This liquid was poured into a mold with a 5 mm thick polyvinyl chloride spacer placed around two glass plates and tightly tightened with a clamp, and heated to 70°C to 150°C in a hot air oven for polymerization. The temperature was raised over 2 hours to carry out polymerization. Thereafter, it was cooled and released from the mold to obtain a transparent resin plate with a smooth surface. Example 4 To 201 parts of 3-isopropenyl-α,α-dimethylbenzyl isocyanate, 0.0 parts of dibutyltin dilaurate was added.
Add 5 parts and heat until the internal temperature reaches 60℃.
32 parts of ethylene glycol was gradually added to carry out a urethanization reaction to obtain a monomer (Chemical formula 19) having the following structural formula.

[0034]

embedded image To this, 61 parts of pentaerythritol tetrakis(3-mercaptopropionate) and 176 parts of pentaerythritol tetraacrylate were added, and further, 2.3 parts of t-butylperoxy-2-ethylhexanoate was added. Added, mixed well and defoamed to make a homogeneous liquid. This solution was poured into a mold with a 5 mm thick polyvinyl chloride spacer placed around two glass plates and tightly tightened with a clamp, and heated from 70°C to 150°C in a hot air oven for polymerization. The temperature was raised over time to carry out polymerization. Thereafter, it was cooled and released from the mold to obtain a transparent resin plate with a smooth surface. Example 5 To 201 parts of 4-isopropenyl-α,α-dimethylbenzyl isocyanate, 0.0 parts of dibutyltin dilaurate was added.
Add 5 parts and heat until the internal temperature reaches 60℃.
After urethanization reaction was carried out by gradually adding 40 parts of methanol, excess methanol was distilled off to obtain a monomer (Chemical formula 20) having the following structural formula.

[0035]

embedded image To this, 90 parts of diethylene glycol bis(2-mercaptoacetate) and 338 parts of trimethylolpropane trimethacrylate were added, and further, 3.3 parts of t-butylperoxy-2-ethylhexanoate were added. The mixture was mixed and defoamed to make a homogeneous liquid. This solution was poured into a mold with a 5 mm thick polyvinyl chloride spacer placed around two glass plates and tightly tightened with a clamp, and heated from 70°C to 150°C in a hot air oven for polymerization. The temperature was raised over time to carry out polymerization. Thereafter, it was cooled and released from the mold to obtain a transparent resin plate with a smooth surface. Example 6 Monomer (chemical formula 16) 110 obtained in the same manner as in Example 1
and a monomer (Chemical formula 19) obtained in the same manner as in Example 4
156 parts of t-
Butyl peroxy-2-ethylhexanoate 3.3
of the mixture was added, mixed well, and defoamed to form a homogeneous liquid. This solution was poured into a mold with a 5 mm thick polyvinyl chloride spacer placed around two glass plates and tightly tightened with a clamp, and heated from 70°C to 150°C in a hot air oven for polymerization. The temperature was raised over time to carry out polymerization. Then cool,
It was released from the mold to obtain a transparent resin plate with a smooth surface.

Comparative Example 1 In Example 1, Example 1 was prepared without adding ethylene glycol bis(3-mercaptopropionate).
Polymerization was carried out in the same manner as above to obtain a transparent resin plate with a smooth surface. Comparative Example 2 In Example 2, polymerization was carried out in the same manner as in Example 2 without adding 1,6-hexanedithiol to obtain a transparent resin plate with a smooth surface. Comparative Example 3 In Example 3, pentaerythritol tetrakis (
Example 3 without adding 3-mercaptopropionate)
Polymerization was carried out in the same manner as above to obtain a transparent resin plate with a smooth surface. Comparative Example 4 In Example 4, pentaerythritol tetrakis (
Example 4 without adding 3-mercaptopropionate)
Polymerization was carried out in the same manner as above to obtain a transparent resin plate with a smooth surface. Comparative Example 5 Polymerization was carried out in the same manner as in Example 5 without adding diethylene glycol bis(3-mercaptopropionate) to obtain a transparent resin plate with a smooth surface. Comparative Example 6 In Example 6, pentaerythritol tetrakis (
Example 6 without adding 3-mercaptopropionate)
Polymerization was carried out in the same manner as above to obtain a transparent resin plate with a smooth surface. Comparative Example 7 Commercially available typical optical plastic PMMA (methyl methacrylate polymer) plate Examples 1 to 6 and Comparative Example 1
Transparent resin plate obtained in ~6 and PMM of Comparative Example 7
Various physical properties of Plate A were measured. The results are shown in Table 1
(Table 1) and Table 2 (Table 2).

[0037]

[Table 1]

[0038]

[Table 2] Various physical properties were measured using the following measuring method. (1) Appearance: The plate-like polymer was visually observed and evaluated. Items with no cracks or surface roughness are marked as (○), and others are marked as (×). (2) Surface hardness: Measured using a paint film pencil scratch tester according to JIS-K-5401. (3) Heat resistance: After being left in a hot air dryer at 120°C for 4 hours, the polymer was taken out, and those with no coloration or surface distortion observed with the naked eye (○), those without (
x). (4) Chemical resistance: After being immersed in isopropanol and toluene for 24 hours at room temperature, those that left no marks with a pencil HB were rated as (○), and those that did not were rated as (x). (5) Workability: Items that can be ground with a beading machine for eyeglass lens processing are marked (○), and items that cannot be ground are marked (x). (6) Impact resistance: Tested without notches according to JIS-K-7111 hard plastic Charpy impact test.

[0039]

[Effects of the Invention] The high hardness transparent resin of the present invention can easily control polymerization, maintains high surface hardness, that is, scratch resistance, heat resistance, and chemical resistance, and has significantly improved impact resistance. It is a resin. Therefore, plate-like polymers made of this resin can be used as glazing materials for windows of vehicles, residences, schools, sports facilities, etc., veranda wainscoting, balconies, various instrument panels, computer displays, LCD televisions, vending machine front panels, etc. For protective covers for display devices, etc.
Lenticular polymers also have excellent performance as optical lenses.

Claims (6)

[Claims] Claim 1: One molecule contains the following general formula (I) (chemical formula 1
) [Chemical 1] and the following general formula (II) or (II
I) (Chemical formula 2) Copolymerizing a monomer (A) having a functional group represented by [Chemical formula 2] and a monomer (B) having two or more -SH groups in one molecule. A high-hardness transparent resin with improved impact resistance. [Claim 2] Monomer (A) and monomer (B) according to Claim 1, and a monomer having at least one functional group selected from the following group (Chemical formula 3) [Claim 3] Quantity (
A high hardness transparent resin with improved impact resistance obtained by copolymerizing with C). Claim 3: The following general formula (IV) (Chemical formula 4) [Chemical formula 4] (wherein, or an aliphatic residue, alicyclic residue, or a heterocyclic residue with or without an aromatic ring, n represents an integer of 1 to 4, and when n = 1, X is an oxygen atom or a sulfur atom, n When ≧2, X is all oxygen atoms, all sulfur atoms, or one or two
monomer (D) in which one is an oxygen atom and the rest is a sulfur atom, or one is a sulfur atom and the rest is an oxygen atom)
and a monomer (E) having m functional groups of at least one type selected from the following group group (Chemical formula 5) [Chemical formula 5] in one molecule, where (n+m) is an integer of 3 or more. A highly hard transparent resin with improved impact resistance obtained by copolymerizing a monomer (B) having two or more -SH groups in one molecule. 4. A glazing material comprising the highly hard transparent resin according to claim 1, 2 or 3. 5. A protective cover for a display device made of the highly hard transparent resin according to claim 1, 2 or 3. 6. An optical lens made of the highly hard transparent resin according to claim 1, 2 or 3.