JPH0641334A - Compoiste transparent formed article - Google Patents

Abstract

(57) [Summary] [Structure] On the surface of a transparent resin molded product having a total visible light transmittance of 85% or more, a pencil hardness of 4H or more, a Rockwell M scale hardness of 100 or more, and a total visible light transmittance of 85% or more. A composite transparent molded article having a bending elastic modulus of 350 kgf / mm ² or more, which is obtained by laminating a transparent resin having a hardness of 0.2 mm or more. [Effect] A resin molded product that has wide surface hardness, excellent scratch resistance, rigidity, impact resistance, heat resistance, chemical resistance and weather resistance, and that can be widely used as a glazing material in industry. To provide a polymerizable monomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite transparent molded article and a novel polymerizable monomer. The composite transparent molded article of the present invention includes outer windows of vehicles, railways, aircrafts, etc. for which visibility, protection and safety are required, windows of partition boards in these vehicles and aircraft, and other various buildings. It is useful as a glazing material for exterior windows of buildings and buildings, and its members for wide lighting from roofs, ceilings, and parts of walls, or as a protective cover for instrument panels and various devices. It is a new transparent material. Further, the polymerizable monomer of the present invention is a monomer of a resin which is useful as a raw material of a high hardness transparent resin and can be a raw material of the composite transparent molded article of the present invention.

[0002]

2. Description of the Related Art Inorganic glass, not to mention its transparency,
It is used in a wide range of fields as a transparent material due to its excellent physical properties. However, it is considered to be a safety issue that it is easily broken and the shape of the fragments when it is broken is dangerous. Furthermore, in recent years, there has been a demand for reducing the weight of various members, and there is an increasing tendency to replace the inorganic glass with a transparent resin or a composite resin.
Until now, molded products of transparent thermoplastic resin, especially molded products of polymethylmethacrylate resin, polycarbonate resin, etc., have excellent transparency and mechanical properties, especially impact resistance, and also have good processability and productivity. It is also used as a glazing material, as a glazing material, as a window and roof of buildings such as various educational and cultural facilities and sports facilities, or in buildings such as station buildings. It is used as a protective wall for highway shelters and aquarium tanks. Further, it is also used as a protective cover for liquid crystal devices, lighting equipment, display devices such as computer displays, or as a signboard or display board.

However, since these resins are linear polymers, the surface hardness, rigidity, heat resistance and chemical resistance of the molded product are not always sufficient. Therefore, in order to improve these physical properties, a hard coat treatment with a silicone-based resin or an acrylic-based resin is generally performed, but from the viewpoint of chemical resistance, the solvent used is selected from a very limited range of types. There must be. The current coating technology has a problem that the thickness of the coating film is limited to about 0.1 mm at most. Depending on the coating material, the surface hardness and chemical resistance of these resins are considerably improved, but if the coating film has such a thickness, improvement in heat resistance and rigidity cannot be expected. Therefore, when using a molded body of these resins as various members, it is necessary to make a thick molded body in order to prevent deformation due to external pressure or wind pressure due to insufficient rigidity. Diethylene glycol diallyl carbonate resin is widely known as a resin that is transparent, has excellent surface hardness, and has improved impact resistance. However, this resin has a problem that the volumetric shrinkage rate during polymerization is large (14%) and that it takes a long time to complete the polymerization, and the impact resistance of the resin is still insufficient. Thus, a resin that can be used as a transparent material such as a glazing material has not been found yet.

As a solution to the above-mentioned problems, a composite resin obtained by laminating molded bodies of transparent resin is disclosed as a transparent material. For example, a polymer and / or copolymer of a (meth) acrylic acid ester-containing polymerizable monomer is used as a base material, and the surface of the polymer has a more flexible (meth) acrylic acid ester polymerization property. A composite resin obtained by coating or injecting a monomer or a prepolymer between two sheets of the base material, polymerizing and stacking them (Japanese Patent Laid-Open No. Sho 53-53).
-2576), in the lamination of the polyurethane layer and the acrylic polymer, both layers are independent layers and at the same time,
A composite resin having a structure in which both layers penetrate into each other (Japanese Patent Application Laid-open No. Sho 6-62).
3-252738), a composite resin obtained by forming a cured film of a ladder-type silicon-based oligomer on the surface of a polycarbonate resin molded body via a (meth) acrylic acid ester copolymer and laminating the cured film (JP-A-3-287634). )
and so on. Further, as a composite resin for the purpose of improving the weather resistance required for a resin which is a transparent material, a composite resin obtained by laminating a highly weather resistant thermoplastic resin on a base material made of an acrylic resin (JP-A-3-30945). ) Technology is also available.

However, these techniques also have some drawbacks in terms of physical properties. That is, in the technique of, although the impact resistance is slightly improved, the surface hardness is still insufficient. In the technique of, when the sheet according to the technique is used alone, it is difficult to secure the rigidity, and With the technique of insufficient hardness, although the surface hardness is improved, the rigidity is poor, but the technique of relatively excellent impact resistance and weather resistance is improved, but the rigidity and the surface hardness are Not satisfactory. Furthermore, polymethyl (meta) is added to the polycarbonate resin molded body with excellent impact resistance.
A composite resin (US-3810815, US-39339) in which heat resistance and weather resistance are imparted by laminating an acrylate resin.
64) technology can also be seen. However, even with this technique, improvement in surface hardness and rigidity cannot be expected. As described above, no resin molded body has been found that satisfies the properties that can be widely used industrially as a glazing material or the like.

[0006]

An object of the present invention is to provide a composite transparent molding which can be widely used in industry as a glazing material and the like, and a novel polymerizable monomer. That is, it is to provide a resin molding having high surface hardness, excellent scratch resistance, rigidity, impact resistance, heat resistance, chemical resistance and weather resistance, and a polymerizable monomer forming the resin.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. As a result, the present invention has been completed. That is, the present invention has a total visible light transmittance of 85%.
On the surface of the above transparent resin molding, pencil hardness of 4H or more,
A composite transparent molded product having a flexural modulus of 350 kgf / mm ² or more formed by laminating a high hardness transparent resin having a Rockwell M scale hardness of 100 or more and a total visible light transmittance of 85% or more to a film thickness of 0.2 mm or more, and Place a new resin molding in the casting polymerization mold, inject the high hardness transparent resin monomer into the space, and polymerize it to obtain the above-mentioned composite transparent molding and transparent resin molding. The present invention relates to the above-mentioned composite transparent molded body obtained by laminating a body and a high-hardness transparent resin molded body. The present invention intends to supplement the insufficient physical properties of the molded product with another resin molded product having excellent physical properties while maintaining the excellent properties of the transparent resin molded product that can be used as a glazing material or the like. To do. That is, in addition to a general-purpose transparent resin molding (hereinafter, transparent resin molding), a high-hardness transparent resin previously proposed by the present inventors (Japanese Patent Laid-Open No. 2-8).
4406, JP-A-3-14804, and JP-A-3-4781.
7, JP-A-3-72513, JP-A-3-179015,
And JP-A-4-266927) by coating with a thickness of 0.2 mm or more by a cast polymerization method, or by laminating a molded body of a high hardness transparent resin having a thickness of 0.2 mm or more by bonding. That is, the composite resin has excellent performance. The transparent resin molded body is relatively excellent in impact resistance, but is insufficient in surface hardness and rigidity, and chemical resistance and heat resistance. Although the hardness transparent resin is excellent in surface hardness and rigidity, chemical resistance and heat resistance, impact resistance is still insufficient. INDUSTRIAL APPLICABILITY The present invention provides a composite transparent resin having extremely excellent performance by making use of the characteristics of a transparent resin molded product and covering the insufficient physical properties as a transparent material such as a glazing material with a high hardness transparent resin. Is what makes it possible.

The composite transparent molded article of the present invention has impact resistance (JI
(Measured by SK-7111) is 7 kgf · cm / cm ² or more,
Flexural modulus of 350 kgf / mm ² or more with excellent surface hardness, scratch resistance, chemical resistance, and heat resistance, total visible light transmittance of 85
%, It is a transparent high-rigidity material showing extremely excellent physical properties of at least%.

The transparent resin molding in the present invention is a resin molding having a total visible light transmittance (according to the ASTM D-1003 method) of 85% or more, and a high hardness transparent resin and the resin molding. A body (hereinafter, collectively referred to as a high-hardness transparent resin) has a total visible light transmittance of 85% or more, a pencil hardness (measured by JIS-K-5400) of 4H or more, and a Rockwell M scale hardness ( 100 or more by the ASTMD-786 method)
It is preferably a resin having a value of 100 to 140.

The composite transparent molded article of the present invention is a laminate of a transparent resin molded article and a high-hardness transparent resin, and the production method thereof has a mutual dissolution protection layer in a casting polymerization mold, or Install a transparent resin molding not having it, inject the monomer of high hardness transparent resin into the space, polymerize and cure,
It is a method of coating with a film thickness of 0.2 mm or more, or a method of laminating a transparent resin molding and a molding of a high-hardness transparent resin having a thickness of 0.2 mm or more via an adhesive layer. The thickness of the high hardness transparent resin layer of the present invention may be 0.2 mm or more, and is preferably 0.5 to 3 mm, although it depends on the type and thickness of the transparent resin molding. In the present invention, the mutual dissolution protection layer means that when a high hardness transparent resin is laminated on a transparent resin molded body by a cast polymerization method, the resin interface of the lamination causes mutual dissolution depending on the combination of the resins, It is a resin that is interposed between both resins in order to prevent the interface from becoming opaque. On the other hand, the adhesive layer is a resin layer having adhesiveness, which is interposed between both resin moldings when the two resin moldings are laminated and laminated.

Examples of the transparent resin molding resin include polymethylmethacrylate resin, polycarbonate resin, polystyrene resin, polyester resin, polyacetal resin, polysulfone resin, polyethersulfone resin, polyvinyl chloride resin, polyvinylidene chloride resin, epoxy resin. Examples thereof include resins, unsaturated polyester resins, polyurethane resins, diallyl phthalate resins, diethylene glycol bisallyl carbonate resins and acetyl cellulose resins. As the resin that forms the mutual dissolution protection layer, polymethylmethacrylate resin, silicone thermosetting resin,
Acrylic thermosetting resin, acrylic photocurable resin, etc., and as the resin for the adhesive layer, polyvinyl butyral resin, melamine resin, epoxy resin, acrylic thermosetting resin, unsaturated polyester resin, polyurethane resin , Vinyl acetate resins, vinyl chloride resins and the like. On the other hand, the high hardness transparent resin is a resin shown below. The high-hardness transparent resin according to the present invention has at least the following formula (1) (formula 16) or the following formula (2) in the resin.
It is a resin having any structure represented by (Chemical Formula 16).

[0012]

[Chemical 16] Specific examples include resins such as Resin-a to Resin-j shown below. The resin-a is represented by a functional group represented by the following general formula (3) (Chemical formula 17) and a general formula (4) (Chemical formula 17) or a general formula (5) (Chemical formula 17) in one molecule. It is a resin obtained by polymerizing a monomer (A) which also has a functional group.

[0013]

[Chemical 17] Resin-b is a monomer (B) having m (m represents an integer of 1 to 6) at least one functional group selected from the following group (Chemical Formula 18) of the monomer (A). It is a resin obtained by copolymerizing and.

[0014]

[Chemical 18] These resin-a and resin-b are represented by the following general formula (1
It is a resin having a structural unit represented by 1) (Chemical formula 19) and / or (12) (Chemical formula 19).

[0015]

[Chemical 19] (In the formula, X represents an oxygen atom or a sulfur atom, and R ₁ represents a hydrogen atom or a methyl group.) Resin-c is a monomer having (A) and two or more —SH groups in one molecule. It is a resin obtained by copolymerizing the body (C). Resin-d is a resin obtained by copolymerizing the monomer (A), the monomer (B) and the monomer (C). Resin-e is a monomer (B) and the following general formula (6).
(N + m) is 3 with the monomer (D) represented by
It is a resin obtained by combining and copolymerizing the above-mentioned integers.

[0016]

[Chemical 20] (In the formula, X represents an oxygen atom or a sulfur atom, R ₂ is a saturated aliphatic residue which may have a halogen atom, an oxygen atom, an alicyclic ring, a heterocycle or an aromatic ring in the residue, Alicyclic residue,
In the heterocyclic residue, n represents an integer of 1 to 4, when n = 1, X is an oxygen atom or a sulfur atom, and when n ≧ 2, X is all oxygen atoms or all sulfur atoms, or 1 Resin-e has the following general formula (13) (Chemical Formula 21) and / or (14) (Chemical Formula 21). ) Is a resin having a structural unit represented by

[0017]

[Chemical 21] (In the formula, R ₁ , R ₂ , X, Y and n have the same meanings as described above, m is an integer of 1 to 6, and (n + m) is 3
The resin-f (representing the above integer) is a combination of the monomer (B) and the monomer (D) so that (n + m) is an integer of 3 or more, and further, the monomer (C) is copolymerized. It is a resin formed. Resin-g has the following general formula (7) (Chemical Formula 2) in one molecule.
A functional group represented by 2) and the following general formula (5)
Or a resin obtained by polymerizing a monomer (E) having a functional group represented by the general formula (8) (Chemical Formula 22),
h is a resin obtained by copolymerizing the monomer (B) and the monomer (E).

[0018]

[Chemical formula 22] (In the formula, R ₁ represents a hydrogen atom or a methyl group) Resin-
g and resin-h are resins having a structural unit represented by the following general formula (15) (Chemical formula 23) and / or (16) (Chemical formula 23).

[0019]

[Chemical formula 23] (In the formula, R ₁ represents the same meaning as described above) The resin-i comprises a monomer (B) and a monomer (F) represented by the following general formula (9) It is a resin obtained by combining and copolymerizing so that (n + m) is an integer of 3 or more.

[0020]

[Chemical formula 24] (In the formula, R ₃ is -C (= O) -NH- group, -C (= S) -NH- group, -C (= O) -O
-Group or a saturated aliphatic residue which may have a functional group selected from -C (= O)-group (provided that each of the functional groups is bonded to an isopropenylphenoxy group on its left side). Group, an alicyclic residue and an aliphatic residue having at least one selected from the group consisting of an alicyclic group, a heterocycle, an aromatic ring and a hetero atom in the residue, or a -C (= O)-group And n is 1 to
Resin-i (representing an integer of 4) is a resin having a structural unit represented by the following general formula (17) (formula 25) and / or (18) (formula 25).

[0021]

[Chemical 25] (In the formula, R ₁ , R ₃ , Y, n and m have the same meanings as described above.) Resin-j is a monomer represented by the following general formula (10) (Chemical Formula 26). It is a resin obtained by copolymerizing the monomer (G).

[0022]

[Chemical formula 26] (In the formula, X is an oxygen atom or a sulfur atom, and R ₄ is an aliphatic residue, an alicyclic residue having or not having an oxygen atom, an alicyclic ring, a heterocycle, or an aromatic ring in the residue. , 1 represents a number of 0 or 1, i and j are integers of 1 or more, and when l = 0, i =
When j = 1 and l = 1, i + j is 4 or less, when j = 1, X is an oxygen atom or a sulfur atom, and when j ≧ 2, X is all oxygen atoms or all sulfur atoms, or 1 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.
It is a resin having a structural unit represented by (Chemical formula 27) and / or (21), (22) (Chemical formula 28).

[0023]

[Chemical 27]

[0024]

[Chemical 28] (In the formula, R ₁ , R ₄ , X, i, j and l have the same meanings as described above.)

Next, the above (resin-a) to (resin-a)
Each monomer used in j) will be described. The monomer (A) having both the functional group represented by the general formula (3) and the functional group represented by the general formula (4) or (5) in one molecule is A compound having at least one functional group of a hydroxyl group or a mercapto group and a functional group represented by the general formula (4) or (5) in one molecule of propenyl-α, α-dimethylbenzyl isocyanate (compound P And a compound P obtained by ring-opening an epoxy group or a thiirane group with acrylic acid or methacrylic acid, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, Hydroxypropyl methacrylate, 1,4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate, Riseroru 1,2 diacrylate, glycerol-1,2-dimethacrylate, glycerol-1,3-diacrylate, glycerol-1,3-dimethacrylate, glycerol-1-acrylate -3
-Ring-opening reaction products of acrylic acid or methacrylic acid of methacrylate, phenylglycidyl ethers, for example 3-phenoxy-2-
Hydroxypropyl acrylate, 3-phenoxy-2
-Hydroxypropyl methacrylate, 2,4-dibromophenoxy-2-hydroxypropyl acrylate,
2,4-dibromophenoxy-2-hydroxypropyl methacrylate, a ring-opening reaction product of acrylic acid or methacrylic acid of bisphenol A-diglycidyl ether, pentaerythritol triacrylate, pentaerythritol trimethacrylate, vinylbenzyl alcohol, vinylthiobenzyl alcohol, Examples thereof include bis (acryloyloxyethyl) isocyanurate and bis (methacryloyloxyethyl) isocyanurate.

The carbamic acid ester or thiocarbamic acid ester is obtained from these by the reaction of the isocyanate group of isopropenyl-α, α-dimethylbenzyl isocyanate with the hydroxyl group or mercapto group of compound P. At this time, a tin compound such as dibutyltin dilaurate or dimethyltin dichloride, or an amine such as morpholine or dimethylaminobenzene may be added so that the synthesis reaction proceeds easily. In order to prevent coloration in the subsequent radical reaction, it is preferable to select a tin compound. When a solvent is used in the reaction, the solvent is distilled off after the synthetic reaction to obtain the monomer (A) without purification.

Specific examples of the monomer (A) include N- (3
-Isopropenyl-α, α-dimethylbenzyl) -2-
Acryloyloxyethyl carbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -2-methacryloyloxyethyl carbamate, N- (4-isopropenyl-α, α-dimethylbenzyl) -2-acryloyloxyethyl carbamate , 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
-Yl carbamate, N- (3-isopropenyl-α,
α-Dimethylbenzyl) -1,3-dimethacryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -1-acryloyloxy-3-methacryloyloxypropane-2
-Yl carbamate, 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-methacryloyloxypropyl carbamate and the like. Examples of the reaction between the isocyanate compound and the mercapto group include compounds in which the above carbamate is changed to thiocarbamate.

M (m represents an integer of 1 to 6) at least one functional group selected from the above group of groups (Formula 18)
The monomer (B) having is a derivative of acrylic acid, methacrylic acid ester or 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, 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,
Examples thereof include bromostyrene, chloromethylstyrene, methoxystyrene and the like.

As m ≧ 2, for example, 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-acryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxydiethoxyphenyl) propane, 2 , 2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-acryloyloxypropyroyloxyphenyl) Propane, 2,2-bis (4-methacryloyloxy propylonitrile yl oxy) 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, hydroxybivalic 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 (acryloyl oxymethyl) isocyanurate, tris (methacryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate,
Dipentaerythritol hexamethacrylate, methyltri (acryloyloxyethoxy) silane, glycerol diacrylate, glycerol dimethacrylate,
Dibromoneopentylglycol diacrylate, dibromoneopentylglycol dimethacrylate, divinylbenzene, urethane acrylates, urethanemethacrylates, 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 can be mentioned.

Examples of the monomer (C) having two or more --SH groups in one molecule include, for example, methanedithiol, 1,2
-Ethanedithiol, 1,1-propanedithiol,
1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanedithiol, 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] hepta-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-dimercaptopropyl 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
-Aliphatic polyols such as mercaptopropionate)

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, 1,2,2 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-anthracene dimethanethiol, 1,3-di (p- Aromatic polyols such as methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane ,

2-methylamino-4,6-dithiol-
sym-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-
Polythiols containing heterocycles such as 4,6-dithiol-sym-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, and the like. Aromatic polythiol containing sulfur atom other than mercapto group such as nuclear alkylated product,

Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio)
Methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-
(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, and their thioglycolic acid and mercaptopropionic acid esters, hydroxymethylsulfide bis (2 -Mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercapto) Acetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxy Till 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-dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate) ), Thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-
Mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4
-Dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3
-Dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid bis (2,3-dimercaptopropyl ester), and other aliphatic compounds containing a sulfur atom in addition to the mercapto group. Examples include heterocyclic compounds containing a sulfur atom in addition to the mercapto group such as polythiol, 3,4-thiophenedithiol, and 2,5-dimercapto-1,3,4-thiadiazole.

The monomer (D) is represented by the above-mentioned general formula (6), and specifically, isopropenyl-α, α-dimethylbenzylisocyanate, a halogen atom, an oxygen atom, and a fatty acid in a residue. A saturated aliphatic residue, an alicyclic residue or a heterocyclic residue with or without an aromatic ring, a heterocyclic ring or an aromatic ring;
A compound having 1 to 4 OH groups or —SH groups, an isocyanate group having isopropenyl-α, α-dimethylbenzyl isocyanate, an —OH group or —SH
Examples thereof include a carbamic acid ester or a carbamic acid thioester compound obtained by reacting with a group. Here, in the general formula (6), when n is 2 or more, X is a compound of all oxygen atoms or sulfur atoms, or one or two oxygen atoms and the rest are sulfur atoms, one is a sulfur atom and the rest are oxygen atoms. Also included are compounds that are: Further, the residue-R generally has a lower molecular weight, but preferably has a molecular weight of the residue portion of 15 to 500, though it depends on the steric rigidity of the structure.

Aliphatic residues and fats used for producing the monomer (D), with or without halogen atom, oxygen atom, alicyclic ring, heterocycle or aromatic ring in the residue. 1 for an -OH group or -SH group with a cyclic or heterocyclic residue
The compound having 4 to 4 includes, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, cyclopentanol, cyclohexanol, 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, - butane diol, 2-ethyl -
1,3-hexanediol, spiroglycol, 1,4
-Cyclohexanediol, tricyclo [5,2,1,
0 ^{2, O} ] decane-4,8-dimethanol, 3-chloro-
1,2-propanediol, 3-bromo-1,2-propanediol, 2,3-dibromo-1,4-butanediol, dibromoneopentyl glycol, bisphenol A (2-hydroxyethyl) ether, bisphenol F (2 -Hydroxyethyl) ether, bisphenol S (2-hydroxyethyl) ether, biphenyl (2-hydroxyethyl) ether, tetrabromobisphenol A (2-hydroxyethyl) 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, glycenol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,6 −
Hexanetriol, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, pentaerythritol, threitol, 3-mercapto-1,2-propanediol, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3 −
Mercaptopropionate) and the like.

To obtain a carbamic acid ester compound or a thiocarbamic acid ester compound using these,
It depends on the reaction between the isocyanate group of isopropenyl-α, α-dimethylbenzyl isocyanate and the —OH group or the —SH method. At this time, a tin compound such as dibutyltin dilaurate or dimethyltin dichloride is used as a catalyst to facilitate the synthesis reaction. Although amines such as morpholine and dimethylaminobenzene may be added, it is preferable to select a tin compound in order to prevent coloration in the subsequent radical reaction. When a solvent is used, the solvent is distilled off after the synthetic reaction. Further, if necessary, purification is performed to obtain a monomer (D). As the monomer (D), specifically, the following general formula (24)
Examples are the compounds represented by (25) (Chemical Formula 30) and (26) (Chemical Formula 31).

[0037]

[Chemical 29]

[0038]

[Chemical 30]

[0039]

[Chemical 31] Further, the following general formulas (27) (formula 32) and (28) (formula 3)
The compounds represented by 3) and (29) (Chemical Formula 34) are also included.

[0040]

[Chemical 32]

[0041]

[Chemical 33]

[0042]

[Chemical 34]

A monomer (E) having both the functional group represented by the general formula (7) and the functional group represented by the general formula (8) or the general formula (5) in one molecule. Is, for example, a compound obtained by reacting isopropenylphenol with acrylic acid, methacrylic acid or an acid chloride thereof, and isopropenylphenol with a functional group represented by the general formula (8) or (5). And a functional group capable of reacting with the phenolic hydroxyl group of isopropenylphenol, for example, —COOH group, —COCl group, halogenated alkyl group, —SO ₃ R (R is an alkyl or aryl group) group, NCO group, -NCS group, epoxy group, etc.
A compound obtained by reacting one or more compounds having one or more compounds, and 1 functional group capable of reacting with isopropenylphenol and a phenolic hydroxyl group possessed by isopropenylphenol.
One or more and one functional group capable of reacting with the —COOH group or the —COCl group of (meth) acrylic acid or an acid chloride thereof, for example, —OH group, —NH ₂ group, halogenated alkyl group and the like. A compound obtained by reacting a compound having the above functions, a compound obtained by reacting the obtained compound with (meth) acrylic acid or an acid chloride thereof, and a ring-opening reaction of a compound having one or more epoxy groups with isopropenylphenol, Examples thereof include compounds obtained by reacting the obtained compound with (meth) acrylic acid or an acid chloride thereof.

A functional group capable of reacting with at least one functional group represented by the general formula (8) or (5) in (1) and a phenolic hydroxyl group of isopropenylphenol, for example, --COOH group, --COCl group, halogen. alkyl group, -SO ₃ R (R is an alkyl or aryl group) group,
Examples of the compound having one or more —NCO group, —NCS group, epoxy group and the like include 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, carboxyphenyl acrylate, carboxyphenyl methacrylate, 2-bromoethyl acrylate, and 2 -Bromethyl methacrylate, chloromethylstyrene, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate and the like are exemplified. In order to obtain the monomer (E) using these, the phenolic hydroxyl group possessed by isopropenylphenol and the
COOH group, the esterification reaction between -COCl group, a halogenated alkyl group, -SO ₃ R (R is an alkyl or aryl group) etherification reaction between groups, -NCO group, -
It can be obtained by a reaction according to a conventionally known method such as a urethanization reaction with an NCS group and a ring opening reaction with an epoxy group.

The isopropenylphenol (1) has at least one functional group capable of reacting with the phenolic hydroxyl group of the isopropenylphenol, and the (-) COOH group or -COCl of the (meth) acrylic acid or the acid chloride thereof.
Functional group capable of reacting with a group, for example, —OH group, —NH ₂
A compound obtained by reacting a compound having at least one group, a halogenated alkyl group, etc. is, for example, an etherification reaction between a compound having two or more halogenated alkyl groups in one molecule and isopropenylphenol. A product and a compound having one or more halogenated alkyl groups, for example, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, bromochloroethane, 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-
A compound which is an etherification reaction product of 5-chloropentane and the like with isopropenylphenol and has one or more halogenated alkyl groups, and one or more halogenated alkyl groups and one -OH group in one molecule. Etherification reaction products of one or more compounds with isopropenylphenol, such as ethylene bromohydrin, ethylene chlorohydrin, 1,3-dibromo-2-propanol, 2,
3-dibromo-1-propanol, 1,3-dichloro-
2-propanol, 3-bromo-1,2-propanediol, 3-chloro-1,2-propanediol, 1-bromo-2-propanol, 3-bromo-1-propanol, 1-chloro-2-propanol, 3-chloro-1-
Etherification reaction product of propanol, 4-chloro-1-butanol and the like with isopropenylphenol, one or more --COOH group, --COCl group and --COBr group in one molecule and one halogenated alkyl group. An esterification reaction product of a compound having both of the above and isopropenylphenol, for example, 3-bromopropionyl chloride, 3-chloropropionyl chloride, 4-bromobutyryl chloride, 4-chlorobutyryl chloride and isopropenylphenol. The esterification reaction product with and the like can be mentioned. The monomer (E) can be obtained by subjecting these to an esterification reaction with (meth) acrylic acid or an acid chloride thereof according to a conventionally known method.

The compound having one or more epoxy groups is, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin,
Epibromhydrin, glycidol, epoxyphenoxypropane, glycidyl acrylate, glycidyl methacrylate, glycidyl isopropyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A Epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid, vinylcyclohexene oxide, N, N-diglycidylaniline, tetraglycidyl diaminodiphenylmethane, triglycidyl p- Aminophenol, diglycidyl hydantoin, triglycidyl isocyanurate, etc. Bets can be, they were ring-opening reaction with isopropenylphenol having the compound obtained -
The monomer (E) can be obtained by esterifying the OH group with a -COOH group or a -COCl group of (meth) acrylic acid or a chloride thereof by a reaction according to a conventionally known method.

Examples of the monomer (E) include the following general formulas (30) (formula 35), (31) (formula 35) and (32).
The compound represented by (Chemical Formula 35) may be mentioned.

[0048]

[Chemical 35]

The monomer (F) represented by the general formula (9) means isopropenylphenol and a --NCO group capable of reacting with the phenolic hydroxyl group contained in the compound,
NCS group, -COOH group, -COCl group, -COBr
Group, a halogenated alkyl group, a —SO ₃ R group (R is an alkyl group or an aryl group), and a functional group such as = SO _{4 and the} like, 1 to 4 functional groups and a saturated aliphatic residue, An alicyclic residue, or an aliphatic residue having at least one selected from the group consisting of an alicyclic group, a heterocycle, an aromatic ring and a hetero atom (nitrogen atom, sulfur atom, oxygen atom, etc.) A compound having the same function or a compound obtained by reacting isopropenylphenol with phosgene, and more specifically, a carbamic acid obtained by reacting a phenolic hydroxyl group of isopropenylphenol with an -NCO group or an -NCS group. Ester compound, carbamic acid thioester compound, -COOH group, -COCl group, ester compound obtained by reaction with -COBr group, -COCl group, by reaction with phosgene Carbonate compound is a halogenated alkyl group, -SO ₃ R group (R alkyl group or an aryl group), an ether compound obtained by reaction of a = SO ₄ group.

Further, the organic group R ₃ in the above general formula (9) is
Generally, a lower molecular weight is preferred, although it depends on steric rigidity, and a residue having a molecular weight of 15 to 500 is preferably used. -NCO group, -NCS group, -NCO group capable of reacting with the phenolic hydroxyl group possessed by isopropenylphenol used when producing the monomer (F),
COOH group, -COCl group, -COBr group, 1 halogenated alkyl group, -SO ₃ R group selected from the group consisting of functional groups such as (R is an alkyl group or an aryl group), = SO ₄ group
Group consisting of 4 functional groups and saturated aliphatic residue, alicyclic residue, or alicyclic group, heterocycle, aromatic ring and hetero atom (nitrogen atom, sulfur atom, oxygen atom, etc.) in the residue The compound having at least one aliphatic residue selected from the group includes, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, cyclohexyl isocyanate, methyl isothiocyanate, ethyl isothiocyanate, propyl isothiocyanate, butyl isocyanate. Thiocyanate, 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 (isopropyl isocyanate), 1,
6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane,
Lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, hexamethylene diisothiocyanate, cyclohexane diisothiocyanate, 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, suberic acid, azelaic acid, sebacic acid, cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, pinic acid , Homopic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, phenylenediacetic acid, oxydiacetic acid, oxaadipic acid, thiodiacetic acid, thiodipropionic acid, dithiodiacetic acid, dithiopropionic acid, and acid chlorides and acids thereof. Bromide, diethylene glycol dichloroformate,

Iodomethane, bromomethane, chloromethane, iodoethane, bromoethane, chloroethane, iodopropane, bromopropane, chloropropane, iodobutane, bromobutane, chlorobutane, iodopentane, bromopentane, chloropentane, iodohexane, bromohexane, chlorohexane, iodoheptane , Bromoheptane, chloroheptane, iodooctane, bromooctane, chlorooctane, iodocyclopentane, bromocyclopentane, chlorocyclopentane, iodocyclohexane, bromocyclohexane, chlorocyclohexane, benzyl chloride, dimethyl sulfate, diethyl sulfate, p-toluene sulfone Acid methyl ester, p-toluenesulfonic acid ethyl ester, diiodoethane, dibromoethane, Chloroethane, diiodopropane, dibromopropane, dichloropropane, diiodobutane, dibromobutane, dichlorobutane, diiodopentane, dibromopentane, dichloropentane, diiodohexane, dibromohexane, dichlorohexane, bromochloroethane, bromochloropropane, chloroiodopropane, Bromochlorobutane, bromochloropentane, bromochlorohexane, α, α′-dibromoxylene, α, α′-dichloroxylene and the like are used. To obtain a carbamic acid ester compound, a carbamic acid thioester compound, an ester compound, a carbonate compound, or an ether compound using these, it is possible to react with the phenolic hydroxyl group possessed by isopropenylphenol-NC
O group, -NCS group, -COOH group, -COCl group, -C
OBr group, halogenated alkyl group, -SO ₃ R group (R is an alkyl group or an aryl group), = SO 1 to 4 functional groups and a saturated aliphatic residue selected from the group consisting of functional groups such as _four , An alicyclic residue, or an aliphatic residue having at least one selected from the group consisting of an alicyclic group, a heterocycle, an aromatic ring and a hetero atom (nitrogen atom, sulfur atom, oxygen atom, etc.) in the residue. It can be obtained by reacting a compound having both of the above or phosgene with isopropenylphenol by a conventionally known method. When a solvent is used, the solvent is distilled off after the synthetic reaction. Further, if necessary, purification is performed to obtain a monomer (F). Specific examples of the monomer (F) include the following general formulas (33) (formula 36) and (34) (formula 3)
6), (35) (Chemical 37), (36) (Chemical 38), (3
7) (Chemical Formula 38) and (38) (Chemical Formula 39) and the like are exemplified.

[0052]

[Chemical 36]

[0053]

[Chemical 37]

[0054]

[Chemical 38]

[0055]

[Chemical Formula 39]

Specific examples of the monomer (G) represented by the general formula (10) include isopropenylphenol and isopropenyl-α, α.
-A compound obtained by subjecting dimethylbenzyl isocyanate to a carbamate esterification reaction between the phenolic hydroxyl group of isopropenylphenol and the isocyanate group of isopropenyl-α, α-dimethylbenzylisocyanate, and oxygen in the residue Compounds having one or more epoxy groups or thiirane groups in an aliphatic residue or an alicyclic residue having or not having an atom, an aliphatic ring, a heterocyclic ring, or an aromatic ring are ring-opened with isopropenylphenol. To the -OH group or -SH group produced by the ring-opening reaction, isopropenyl-
Compound obtained by subjecting α, α-dimethylbenzylisocyanate to isocyanate group carbamic acid esterification reaction or thiocarbamic acid esterification reaction, whether residue has oxygen atom, aliphatic ring, heterocycle or aromatic ring The aliphatic residue and alicyclic residue which do not have both have at least one halogenated alkyl group capable of reacting with the phenolic hydroxyl group of isopropenylphenol, and at least one -OH group and / or -SH group. Compound and isopropenylphenol are etherified with a halogenated alkyl group and a phenolic hydroxyl group of isopropenylphenol, and further -OH group and / or -SH
And a compound obtained by subjecting an isocyanate group of isopropenyl-α, α-dimethylbenzyl isocyanate to a carbamic acid esterification reaction and / or a thiocarbamic acid esterification reaction, and the like.

Further, the residue R ₄ in the general formula (10) is
Generally, a lower molecular weight is preferable, although it depends on the three-dimensional rigidity of the structure.
~ 500 is preferably used. A compound having one or more and two or less epoxy groups or thiirane groups in an aliphatic residue or an alicyclic residue having or not having an oxygen atom, an aliphatic ring, a heterocyclic ring or an aromatic ring in the above residue. And, for example, ethylene oxide, propylene oxide, 2,3-epoxybutane, 3,4-epoxybutane, 2,3-epoxypentane, 1,2-epoxyhexane, epoxycyclohexane, epoxycycloheptane, epoxycyclooctane, styrene. Oxide, 2-phenyl-1,2-epoxypropane, tetramethylethylene oxide, epirochlorohydrin, epibromohydrin, glycidol, 1,2-epoxy-3-phenoxypropane, glycidyl isopropyl ether, ethylene sulfide, propylene sulfide, Isobutene sulfide, 2,3
Butylene sulfide, styrene sulfide, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, spiroglycol diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A epoxy resin, tetrabromobisphenol A epoxy Resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, vinyl cyclohexene dioxide, phthalic acid diglycidyl ester, tetrahydrophthalic acid Diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p Oxy benzoic acid, malonic acid diglycidyl ester, succinic acid diglycidyl ester, glutaric acid diglycidyl ester, adipic acid diglycidyl ester, N, N-diglycidyl aniline, and the like diglycidyl hydantoin.

An aliphatic residue having or not having an oxygen atom, an aliphatic ring, a heterocyclic ring or an aromatic ring in the residue, or a halogen capable of reacting with the phenolic hydroxyl group of isopropenylphenol in the alicyclic residue. One or more alkylated groups,
The compound having one or more OH groups and / or --SH groups includes, for example, iodoethanol, bromoethanol, bromopropanol, 3-bromo-1,2-propanediol, bromohexanol, chloroethanol,
Chloropropanol, 3-chloro-1,2-propanediol, chlorobutanol, chlorohexanol, 1,
4-dibromo-2,3-butanediol, 2,3-dibromo-1,4-butanediol, 1,4-bromo-2-
Butanol, 1,3-dibromo-2-propanol,
2,3-dibromopropanol, 1,3-dichloro-2
-Propanol, dibromoneopentyl glycol, chloropropane thiol and the like.

Using these, using the known carbamate esterification reaction, thiocarbamate esterification reaction, etherification reaction, ring-opening reaction of epoxy group or thiirane group, etc., as described in the above, The monomer (G) can be obtained. When a solvent is used, the solvent is distilled off after the synthetic reaction. Further, if necessary, purification is performed to obtain a monomer (G). Specific examples of the monomer (G) include the following general formulas (39) (formula 40) and (40) (formula 4)
Examples thereof include compounds represented by 0).

[0060]

[Chemical 40]

The high hardness transparent resin used in the present invention can be obtained by polymerizing the above-mentioned monomers. The monomer (A) is a monomer that can be polymerized alone, and by homopolymerization to give (resin-a), and by copolymerizing with the monomer (B) (resin-b). )give. The ratio of the monomer (A) to the monomer (B) in the copolymerization cannot be unconditionally determined depending on the type of functional group of each monomer and the structure of the monomer. Is based on 1 equivalent of the isopropenylphenyl group in the monomer (A).
It is preferable that the total sum of 1) is in the range of 0.5 to 10 equivalents.

[0062]

[Chemical 41] Further, the monomer (A) is copolymerized with the monomer (C) to give (resin-c) having improved impact resistance as compared with (resin-b).

By copolymerizing the monomers (A), (B), and (C), (resin-d) having improved impact resistance as compared with (resin-c) can be obtained. . The ratio of the monomers at the time of this copolymerization cannot be unconditionally determined depending on the type of functional group of each monomer and the structure of the monomer. In the mixture of the monomers, the isopropenylphenyl group of the monomer (A), the —SH group of the monomer (C), and the monomer (A) and the monomer (B) are The ratio with respect to the total of the above-mentioned group of groups (Chemical Formula 41) that each has is not unconditionally determined depending on the kind of functional group contained in the monomer and the structure of the monomer, but the ratio of —SH group is small. And a sufficient improvement in impact resistance is not seen, on the contrary, if it is too much, the polymer becomes rubbery,
Surface hardness and rigidity are significantly reduced. Further, if the ratio of the above group (Chemical Formula 41) is small, a polymer will not be obtained, and if it is too large, it will be difficult to control the polymerization. The proportion used in the copolymerization is such that the amount of —SH group is 1 equivalent of isopropenylphenyl group.
It is usually 0.1 to 5 equivalents, preferably 0.3 to 1.5 equivalents, and the total sum of the above group (Chemical Formula 41) is usually 0.3 to
It is in the range of 10 equivalents, preferably 0.5 to 6 equivalents. The monomer (D) is a monomer that cannot be polymerized by itself, and by copolymerizing with the monomer (B), (resin-e) is provided. The ratio of copolymerization of the monomer (D) and the monomer (B) in this copolymerization conforms to the ratio of the monomer (A) and the monomer (B). Further, by copolymerizing the monomer (D), the monomer (B) and the monomer (C), a (resin-f) having improved impact resistance as compared with the (resin-e) is provided. The copolymerization ratio of the monomers in this copolymerization is as follows:
According to the ratio of (B) and (C).

The monomer (E) is a monomer which is curable alone, and gives (resin-g) by homopolymerization. Further, the monomer (E) is copolymerized with the monomer (B) to give (resin-h). The copolymerization ratio of the monomer (E) and the monomer (B) in this copolymerization conforms to the ratio of the monomer (A) and the monomer (B). Monomers (F) and (G) are monomers that cannot be polymerized alone,
Copolymerization with the monomer (B) gives (resin-i) and (resin-j), respectively. The ratio of the copolymerization of the monomer (F) or (G) and the monomer (B) in this copolymerization conforms to the ratio of the monomer (A) and the monomer (B).
Further, it is naturally possible to obtain a high-hardness transparent resin composed of two or more kinds of the above-mentioned resin groups by mixing and polymerizing and curing the monomers that give each resin.

The composite transparent molded article of the present invention is obtained by injecting a monomer to be a high hardness transparent resin into the space between the transparent resin molded article placed in the casting polymerization mold and the mold, It is obtained by a method of polymerizing and laminating, or a method of laminating a molded body of a high-hardness transparent resin obtained by polymerizing a monomer to be a high-hardness transparent resin to a transparent resin molded body and laminating it. The polymerization of the monomer that becomes the high hardness transparent resin of the present invention is radical polymerization. As the polymerization method, not only thermal polymerization but also a method using ultraviolet rays, γ rays, or the like can be used, or a combination thereof can be used. However, the thermal polymerization method is particularly preferred. The radical polymerization initiator at the time of performing thermal polymerization is not particularly limited, and known benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, t-butylperoxypivalate. And azo compounds such as azobisisobutyronitrile can be used, and the amount thereof is 0.01 to 5% by weight.
Photosensitization in the case of ultraviolet curing is not particularly limited, and known benzoin compounds, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether,
Benzoin isobutyl ether, 2-hydroxy-2-benzoinpropane, azobisisobutyronitrile, benzyl, thioxanthone, diphenyl disulfide and the like can be used, and the amount thereof is 0.01 to 5% by weight. When using radiation such as γ-rays, a polymerization initiator or the like is generally not always necessary. In the thermal polymerization, the heating temperature is 50
To 200 ° C. and 1 to 8 hours. Polymerization when the high-hardness transparent resin is used alone, or polymerization when the transparent molded body and the high-hardness transparent resin are combined, is performed under optimum polymerization conditions in each case. In addition, in the liquid or mixed liquid of the monomers before the polymerization, an additive such as an ultraviolet absorber, an antioxidant, a coloring inhibitor, a fluorescent dye or a near infrared absorber, or another reactive monomer is appropriately used in advance. You may add. The monomer liquid or mixed liquid thus prepared is subjected to defoaming treatment, if necessary.

Next, a method for compounding the resin, that is, a method for producing the composite transparent molded article of the present invention will be specifically described below. First of all, it is a casting polymerization method, but in this method, a transparent resin molding is set in a casting polymerization mold, and a monomer of a high-hardness transparent resin is injected into the space portion thereof to carry out polymerization. Is a method for obtaining a composite transparent molded body. Here, the casting polymerization mold means that a gasket is arranged around each of the two moldings having the same shape as the molding material, and a transparent resin molding and the molding material are provided on the inner and adjacent portions thereof. A spacer for providing a space is provided between the transparent resin molding and the transparent resin molding so that the high-hardness transparent resin layer can be laminated to a desired thickness. Two pieces of the mold material having such a form are integrated so that the gasket surfaces of both are in close contact with each other, and the periphery of this is fixed by a fixing tool such as a clip. At this time, part of the gasket can be opened and closed before and after the monomer injection.
The part is left unfixed until the monomer is injected.
Further, when the high-hardness transparent resin is laminated only on one surface of the transparent resin molded body, the spacer may be arranged only on one surface of the mold material. The material of the mold material may be any of general-purpose metals, for example, iron, copper, aluminum, or alloys such as brass, or glass, or composite resin such as glass fiber reinforced plastic or carbon fiber reinforced plastic. it can. The point is that the surface is smooth and does not interact with the injected high-hardness transparent resin monomer, for example, corrosion of the template by the monomer, alteration of the monomer by elution components from the template, or monomer. Any material that does not cause permeation of In the case of thermal polymerization, it may be altered by the heat,
It should not be dimensionally stable. The material of the gasket is required to have chemical resistance and heat resistance, do not allow the monomer to permeate, and have appropriate flexibility. For example, as the resinous material, a tube or sheet of vinyl chloride resin, silicone resin or the like can be used. Further, the thickness of the gasket is set to be slightly thicker than the desired thickness of the composite transparent molded body in consideration of slight shrinkage of the high-hardness transparent resin during curing. The material of the spacer may be the same as the gasket and the same shape, but other general-purpose resin sheets can also be used. Also, the thickness of the spacer is made slightly thicker than the desired thickness of the high-hardness transparent resin layer to be laminated on the transparent resin molding for the same reason. The shape of the mold must match the shape of the desired composite transparent molding. According to the polymerization method of the present invention, the resin can be compounded not only with a flat surface but also with a curvature. Therefore, the shape of the mold can be freely designed and selected according to the desired shape of the composite transparent molded body. Here, in order to obtain a composite transparent molded product having a curvature, it is necessary to prepare a transparent transparent resin molded product as a base material of the composite transparent molded product in advance. After placing the transparent resin molding between the two molding materials in the hot-air stove, the transparent resin molding is easily heated by heating at a temperature near the glass transition temperature (Tg) for 1 to 2 hours. can get. In this method, if necessary, a release agent such as an internal release agent or an external release agent may be used.

Next, the transparent resin molding will be described.
The molded body is a polymethylmethacrylate resin, a polycarbonate resin, a polystyrene resin, a polyester resin,
Polyacetal resin, polysulfone resin, polyether sulfone resin, polyvinyl chloride resin, polyvinylidene chloride resin, epoxy resin, unsaturated polyester resin,
It can be selected from molded articles made of polyurethane resin, diallyl phthalate resin or diethylene glycol bisallyl carbonate resin. The size of the molded body is a size that matches the desired composite transparent molded body. However, if the thickness is too thin, the fixing stability at the time of polymerization will be insufficient, so a thickness of 0.2 mm or more is preferable.
The case where the transparent resin molding has a mutual dissolution protection layer will be described. As described above, the resin forming the mutual dissolution protection layer can be selected from polymethylmethacrylate resin, silicon thermosetting resin, acrylic thermosetting resin or acrylic photocurable resin. The mutual dissolution protection layer made of a resin selected from these may be in the form of a sheet or a coat. As a method for laminating these on a transparent resin molded body, in the case of a sheet-shaped one, it may be carried out by bringing it into close contact with the surface of the transparent resin molded body and performing a heat fusion method which is usually performed. On the other hand, in the case of a coat, a transparent resin molding may be dipped in a solution prepared by dissolving the resin in a suitable solvent, and then the solvent may be removed and then heat-cured or photocured. . At this time, the thickness of the mutual dissolution protection layer is sufficient as long as it can prevent opacity due to mutual dissolution at the laminated interface between the transparent resin molding and the high-hardness transparent resin. It will never be thicker than that. Although depending on the combination of both resins, 2 μm to 100 μm is usually sufficient.

Next, a method of laminating a transparent resin molding and a high-hardness transparent resin molding through an adhesive layer will be described. As described above, the resin forming the adhesive layer is made of polyvinyl butyral resin, melamine resin, epoxy resin, acrylic thermosetting resin, unsaturated polyester resin, polyurethane resin, vinyl acetate resin and vinyl chloride resin. You can choose. Then, an adhesive made of these resins is applied to either the surface of the transparent resin molded body or the high-hardness transparent resin molded body, or to the surface of each of the two resins, and then the adhesive layer is placed inside. Both resins are made to face each other and are bonded. Here, as a bonding method, although it depends on a resin as an adhesive, it is usually placed in an autoclave for defoaming under reduced pressure, and then heating and pressurizing. Heating temperature is 40-120 ℃, pressure is 5-10kgf /
It is cm ² . Here, the high-hardness transparent molded body used for the main bonding may be manufactured according to the above-mentioned method for manufacturing the composite transparent molded body by the cast polymerization method. That is, the monomer of the high-hardness transparent resin may be injected and polymerized in the space portion of the casting polymerization mold in which the gasket having the thickness corresponding to the desired thickness of the high-hardness transparent resin molding is arranged. .

The physical properties of a resin required for a material such as a glazing material provided by the present invention are mechanical properties such as high impact resistance as well as high surface hardness, scratch resistance and rigidity. . That is, for a general-purpose transparent resin molded body, both impact resistance and hardness characteristics such as surface hardness, which are difficult to achieve, are required. As a means for solving the above problems, usually, impact resistance, or the characteristics of hardness such as surface hardness, resins having each independently, a method of blending on a monomer basis of the resin, or blended on a polymer basis However, in these cases, the respective properties of both resins cannot be maintained, and rather, the properties tend to weaken each other in many cases. In addition, due to advances in hard coating technology, there is also a means of hard coating resin molded products that have impact resistance, and although surface hardness has been attempted to be improved considerably, due to the technical limit of the thickness of the coating film, As I mentioned earlier, I cannot say that I can hope for improvement.

The inventors of the present invention have conducted extensive studies to satisfy the contradictory characteristics such as impact resistance and hardness such as surface hardness at the same time. It was found that by stacking this resin on a transparent resin molded body, a resin molded body having the characteristics of both resins can be obtained as a result. The composite transparent molded article of the present invention has impact resistance and
While maintaining the characteristics of hardness such as surface hardness,
It is a resin that also has chemical resistance and heat resistance, and has a flexural modulus of 3
It is an extremely excellent molded product having 50 kgf / mm ² or more.

The reason why the thickness of the high-hardness transparent resin layer of the composite transparent molded article of the present invention is 0.2 mm or more is that the thickness of the high-hardness transparent resin layer is as a result of detailed study by the present inventors. , 0.2
This is because the flexural modulus of the molded body of mm or less does not exceed 350 kgf / mm ^2, and the high rigidity of the high hardness transparent resin cannot be imparted to the composite transparent molded body. The present inventors have conducted a detailed study on the method of compounding a transparent resin molding and a high-hardness transparent resin, and evaluating the physical properties of the obtained composite resin molding. It has been found that the molded product is particularly excellent.
That is, the transparent resin molded body is a polymethylmethacrylate resin molded body, a polycarbonate resin molded body, or a polycarbonate resin molded body having a polymethylmethacrylate resin or an acrylic photocurable resin as a mutual dissolution protective layer. Is a composite transparent molded body obtained by laminating a high-hardness transparent resin, which is any one of the above-mentioned (resin-a), (resin-b), and (resin-d), onto the resin molded body according to the casting polymerization method. .

Now, the novel polymerizable monomer, which is another object of the present invention, will be described. The industrial technical field of the present polymerizable monomer can be used in the same range as that of the high hardness transparent resin previously proposed by the present inventors and used in the present invention. It is a polymerizable monomer that is useful as a raw material. The present inventors, while maintaining the excellent properties of the high hardness transparent resin proposed above, by imparting more flexibility, in order to improve the impact resistance, as a result of searching a polymerizable monomer, The novel polymerizable monomer of the present invention has been found. The polymerizable monomer of the present invention has the following general formula (23)
It is a polymerizable monomer represented by.

[0073]

[Chemical 42] (In the formula, k is an integer of 2 to 10, R ₅ and R ₆ each represent a hydrogen atom or a methyl group, and the position of the aromatic ring is the p-position,
The monomer of the present invention is a (meth) acrylic acid monoester of polyethylene or polypropylene glycol represented by the following general formula (Chemical Formula 43):
Obtained by reaction with (4) -isopropenyl-α, α-dimethylbenzyl isocyanate.

[0074]

[Chemical 43] (In the formula, k is an integer of 2 to 10, R ₅ and R ₆ are each a hydrogen atom or a methyl group.) As (meth) acrylic acid monoester of polyethylene or polypropylene glycol, polyethylene glycol monoacrylate or polyethylene glycol mono is used. Methacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate may be mentioned. The reaction is
3-isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate 0.8-1. To 1 mol of (meth) acrylic acid monoester of polyethylene or polypropylene glycol. 1 mol, preferably 0.
95 to 1.05 mol was added, and the reaction temperature was 20 to 80 ° C.
The temperature is preferably maintained at 30 to 60 ° C., and a catalyst-free or urethane-promoting catalyst such as dibutyltin dilaurate is added in an amount of 0.001 to 5% by weight, preferably 0.05 to 1% by weight, based on the weight of the isocyanate. . After completion of the reaction, the reaction solution can be purified by column chromatography to obtain the polymerizable monomer of the present invention.

[0075]

EXAMPLES The present invention will now be described with reference to specific examples of a method for producing a composite transparent molded article, that is, a casting polymerization method, a laminating method, and a novel polymerizable monomer. And describe in detail. The present invention is not limited to these.
Moreover, the part in an Example represents a weight part. The evaluation methods of the transparent moldings used in the examples and the obtained composite transparent moldings are shown below. -Transparent molding used in Examples 1. Molded polymethylmethacrylate resin: Sumipex manufactured by Sumitomo Chemical Co., Ltd. 2. Polycarbonate resin molding: Mitsubishi Gas Chemical Co., Ltd.
Made Iupilon sheet NF-2000-U 3. 3. Polycarbonate resin molded product having polymethylmethacrylate resin as mutual dissolution protective layer: Iupilon sheet L-55 manufactured by Mitsubishi Gas Chemical Co., Inc. 4. Molded polyvinyl chloride resin: ADEKA ARGUS CORPORATION
Made 5. Epoxy resin molding: Diglycidyl ether of bisphenol A manufactured by Yuka Shell Epoxy Co., Ltd. (trade name:
250 parts of Epikote 828), 200 parts of methylendomethylenetetrahydrophthalic anhydride, and 2.5 parts of a tertiary amine (accelerator) were mixed, and the mixture was poured into a casting polymerization mold. Installed in the hot stove, 1
Molded product obtained by polymerization by heating at 00 ° C. for 2 hours and subsequently at 150 ° C. for 4 hours 6. Polyester resin molding: Pellets of polyethylene terephthalate resin (trade name: Sanpet) manufactured by Asahi Kasei Co., Ltd. are spread in a casting polymerization mold, and this mold is placed in an autoclave to 5 kgf / cm ² . Pressurize, 1
Molded product obtained by heating at 30 ° C. for 2 hours and heat-sealing 7. Diaryl phthalate resin molding: Osaka Soda Co., Ltd.
180 parts of diaryl isophthalate manufactured by Mitsui Toatsu Chemicals, Inc. and 198 parts of diethylene glycol bis (aryl carbonate) (trade name: MR-3) manufactured by Mitsui Toatsu Chemicals, Inc. are mixed, and 11 parts of isopropenyl peroxide as a radical initiator is added to the mixture. 7. A molded product obtained by pouring and adding this monomer into a casting polymerization mold, placing this mold in a hot-air oven, and heating from room temperature to 80 ° C. for 24 hours to polymerize. Polyurethane resin molded product: Sulfur-containing polyurethane resin monomer manufactured by Mitsui Toatsu Chemicals, Inc. (trade name: MR-6)
To 400 parts, 0.04 parts of dibutyltin dichloride was added as a urethanization reaction catalyst, this monomer was injected into a casting polymerization mold, and this mold was placed in a hot stove, and the temperature was 40 ° C to 120 ° C. Molded product obtained by polymerizing by heating for 24 hours. Polyacetal resin molding: Pellets of polyacetal resin (trade name: Tenac) manufactured by Asahi Kasei Co., Ltd. are spread in a casting polymerization mold, and this mold is placed in an autoclave and pressurized to 5 kgf / cm ² . Molded body obtained by heating at 160 ° C. for 2 hours and heat fusion 10. Unsaturated polyester resin molded product: To 400 parts of unsaturated polyester resin monomer (trade name: Ester C type) manufactured by Mitsui Toatsu Chemicals, Inc., 8 parts of benzoyl peroxide was added as a radical initiator, and this monomer was added. It is poured into a casting polymerization mold, placed in a hot air oven, heated from 40 ° C to 100 ° C for 4 hours,
Molded product obtained by polymerization

Evaluation method (1) Appearance: The molded body was visually observed and evaluated. Those with no cracks or surface roughness were marked with (○), and others were marked with (x). (2) Total visible light transmittance: measured according to the ASTM D-1003 method. (3) Surface hardness: Pencil hardness: Measured using a JIS-K-5401 pencil scratch tester for coating film. Vickers hardness: Measured using a Terazawa microhardness meter (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Rockwell M scale hardness: Measured according to the ASTM D-786 method. (4) Impact resistance: The test was performed without notches by the Charby impact test of JIS-K-7111 hard plastic. (5) Flexural modulus: Measured according to JIS-K-7203 method. (6) Heat resistance: After the polymer was left in a hot air dryer at 120 ° C for 4 hours, the polymer was taken out, and when the polymer was not colored or surface strain was not observed with the naked eye (○), the other ( X). (7) Chemical resistance: After being soaked in isopropanol and toluene at room temperature for 24 hours, pencil hardness HB, in both cases, marks that do not leave marks (○), those that do not remain (x) did. (8) Workability: The one that can be ground by the ball-shaving machine for processing spectacle lenses was designated as (◯), and the one that could not be ground was designated as (×).

Example 1 2-Isopropenyl-α, α-dimethylbenzylisocyanate 253.6 parts of dibutyltin dilaurate (0.64 parts) was added as a reaction catalyst, and the internal temperature was maintained at 60 ° C.
After gradually adding 146.4 parts of hydroxyethyl acrylate, urethanization reaction was carried out at the same temperature for 2 hours. As a result, colorless and syrup-like N- (3-isopropenyl-
α, α-Dimethylbenzyl) -2-acryloyloxyethyl carbamate was obtained. Next, 2.53 parts of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to this product, and the mixture was thoroughly stirred and then degassed. Then, this monomer is placed in the center of a mold consisting of two flat glass plates with a thickness of 5 mm and a side length of 400 mm and a silicone rubber gasket, and a thickness of 3 mm,
A molded body of polymethylmethacrylate resin with a side length of 380 mm, and the facing distance between the molded body and the glass plate is 1 each.
After the spacer was installed so as to have a size of mm, it was poured into a fixed mold for polymerization, and then this mold was placed in a hot air oven to carry out polymerization by heating from 60 ° C. to 170 ° C. for 3 hours. Example 2 0.56 parts of dibutyltin dilaurate as a reaction catalyst was added to 227.2 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate, and the internal temperature was maintained at 60 ° C.
Gradually add 105.1 parts of hydroxyethyl acrylate,
Next, 67.7 parts of pentaerythritol triacrylate was gradually added, and then urethanization reaction was carried out at the same temperature for 2 hours. Then, 2.27 parts of t-butylperoxy-2-ethylhexanoate was added as a radical polymerization initiator to the acrylate mixture of the urethane compound, and the mixture was thoroughly stirred and then defoamed. Then, the polymerization of Example 1 was performed using this monomer. Example 3 To 202.4 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 197.6 parts of glycerol-1,3-diacrylate, 0.88 parts of dibutyltin dilaurate was added as a reaction catalyst, while maintaining the internal temperature at 60 ° C. As a result of urethanization reaction for 2 hours, colorless and syrupy N-
(3-isopropenyl-α, α-dimethylbenzyl)-
1,3-Diacryloyloxypropan-2-ylcarbamate was obtained. Next, 0.4 parts of lauroyl peroxide and 2.0 parts of benzoyl peroxide were added to this product as a radical polymerization initiator, and after thoroughly stirring,
Defoaming was performed. Then, the polymerization of Example 1 was performed using this monomer.

Example 4 105.1 parts of trimethylolpropane triacrylate,
To 186.9 parts of 3-isopropenyl-α, α-dimethylbenzylisocyanate, 1.33 parts of dibutyltin dilaurate as a reaction catalyst was added, and while maintaining the internal temperature at 60 ° C, 2
-Hydroxyethyl acrylate 108.0 parts was gradually added, and then urethanization reaction was performed at the same temperature for 2 hours.
Then, t-butylperoxy-2- was used as a radical polymerization initiator in the acrylate mixture of the urethane compound.
Ethyl hexanoate (4.64 parts) was added and well mixed, and then defoamed. Then, the polymerization of Example 1 was performed using this monomer. Example 5 193.9 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate and glycerol-1-acrylate-
After adding 2.03 parts of dibutyltin dilaurate as a reaction catalyst to 206.1 parts of 3-methacrylate, the internal temperature was adjusted to 60 ° C.
As a result of carrying out the urethanization reaction for 1 hour while keeping at, the colorless and syrup-like N- (3-isopropenyl-α, α-
Dimethylbenzyl) -1-acryloyloxy-3-methacryloyloxypropan-2-ylcarbamate was obtained. Next, 0.4 parts of lauroyl peroxide and 2.0 parts of benzoyl peroxide were added as radical polymerization initiators to this product, and the mixture was thoroughly stirred and then degassed. Then, this monomer was poured into a polymerization mold having the same contents as shown in Example 1, this mold was placed in a hot air oven, and polymerization was carried out at 60 ° C. for 1 hour and then at 160 ° C. for 2 hours. Then, after cooling, the mold was taken out to obtain a colorless and transparent molded body. Example 6 To 200.5 parts of 4-isopropenyl-α, α-dimethylbenzyl isocyanate and 199.5 parts of glycerol-1,3-diacrylate, 2.08 parts of dibutyltin dilaurate was added as a reaction catalyst, while maintaining the internal temperature at 60 ° C. As a result of urethanization reaction for 1 hour, colorless and syrupy N-
(4-isopropenyl-α, α-dimethylbenzyl)-
1,3-Diacryloyloxypropan-2-ylcarbamate was obtained. Next, 0.4 parts of lauroyl peroxide and 2.0 parts of benzoyl peroxide were added to this product as a radical polymerization initiator, and the mixture was thoroughly stirred and then defoamed. Then, this monomer was poured into a polymerization mold having the same content as shown in Example 1 and then polymerized under the same conditions as shown in Example 5 to obtain a colorless and transparent molded body.

Example 7 To 182.4 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 18.7 parts of ethylene glycol, 0.08 part of dibutyltin dilaurate was added as a reaction catalyst,
The urethanization reaction was carried out for 1.0 hour while maintaining the internal temperature at 40 ° C. Then, 39.2 parts of 2-hydroxyethyl acrylate was added to this reaction solution, and the urethanization reaction was carried out for 2 hours while maintaining the internal temperature at 50 ° C. Then, after adding 159.7 parts of pentaerythritol tetraacrylate to this reaction solution and stirring well, 0.4 part of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the acrylate mixture of this urethane compound. Then, the mixture was thoroughly stirred and then defoamed. Then, this monomer was used to carry out the polymerization of Example 1 and further at 180 ° C. for 30 minutes. Example 8 To 201 parts of 4-isopropenyl-α, α-dimethylbenzyl isocyanate, 0.5 part of dibutyltin dilaurate was added, and 222 parts of 3-phenoxy-2-hydroxypropyl acrylate was gradually added while heating so that the internal temperature became 60 ° C. In addition to the above, a urethane reaction was performed to obtain a viscous urethane compound. Add 200 parts of methyl acrylate and 3.0 parts of t-butylperoxy-2-ethylhexanoate and stir well, then stir until the internal temperature reaches 50 ° C until the viscosity of the content liquid reaches 150 centipoise. After carrying out prepolymerization, defoaming was carried out under reduced pressure, and using this liquid, the polymerization of the embodiment of Example 1 was carried out. Example 9 300 parts of styrene and 201 parts of p-isopropenyldimethylbenzyl isocyanate and dibutyltin dilaurate
1.0 part was added, and 514 parts of bisphenol A bis (2-hydroxymethacryloyloxypropyl ether) was gradually added while heating to an internal temperature of 60 ° C. to carry out a urethane reaction, and a viscous urethane compound styrene mixture. Got To this, 5.0 parts of t-butylperoxy-2-ethylhexanoate was added and well stirred, and then defoaming was performed under reduced pressure, and the polymerization of Example 1 was performed using this solution.

Example 10 A radical initiator-containing monomer prepared by the same formulation as in Example 1 was added to the center of a mold composed of two glass plates having a thickness of 5 mm, a curvature of 0.02 and a diameter of 300 mm, and a silicone gasket. Injected into a polymerization mold fixed with spacers so that the facing distance between the glass plate and the polymethylmethacrylate resin molded body with a thickness of 3 mm, a curvature of 0.02 and a diameter of 280 mm is 1 mm in each part. Then, this mold was placed in a hot air oven, and polymerization was carried out under the same conditions as shown in Example 1. Example 11 The radical initiator-containing monomer prepared by the same formulation as in Example 3 was replaced with a polycarbonate resin molded body in place of the polymethylmethacrylate resin molded body, and otherwise the same conditions as those in Example 3 were used. Polymerized. Example 12 Polymerization of the embodiment of Example 11 was carried out using the radical initiator-containing monomer prepared in the same formulation as shown in Example 7. Example 13 A radical initiator prepared by replacing the polymethylmethacrylate resin molded body with a polycarbonate resin molded body and otherwise using the same content as shown in Example 10 in a mold having the same formulation as shown in Example 11. The charged monomer was injected, this was placed in a hot air oven, and polymerization was carried out by the same polymerization method as described in Example 11 to obtain a colorless and transparent molded body. Example 14 A monomer containing a radical initiator prepared by the same formulation as shown in Example 12 was poured into a mold having the same contents as shown in Example 13, and this was placed in a hot stove to obtain Example 12.
Polymerization was carried out by the same polymerization method as shown in, to obtain a colorless and transparent molded body. Example 15 The monomer containing a radical initiator prepared in the same formulation as in Example 2 was replaced with a polycarbonate resin molded body having a polymethylmethacrylate resin as a mutual dissolution protective layer, and otherwise the polymethylmethacrylate resin molded body was replaced. After pouring into a mold having the same contents as shown in Example 1, this was placed in a hot air oven and polymerized by heating at 60 to 170 ° C. for 3 hours to obtain a colorless and transparent molded body.

Example 16 A monomer having a radical initiator and prepared in the same manner as in Example 4 was poured into a mold having the same contents as shown in Example 15, which was then placed in a hot stove and heated at 55 ° C. for 1 hour. , Further 160 ℃
Polymerization was carried out for 2 hours to obtain a colorless and transparent molded body. Example 17 A monomer having a radical initiator and prepared in the same manner as in Example 6 was poured into a mold having the same contents as shown in Example 15, which was placed in a hot air stove and further heated at 60 ° C. for 1 hour. ℃
Polymerization was carried out for 2 hours to obtain a colorless and transparent molded body. Example 18 A monomer containing a radical initiator prepared by the same formulation as in Example 7 was poured into a mold having the same contents as shown in Example 15, and the mold was placed in a hot stove to raise the temperature to 60 ° C to 180 ° C. Polymerization was carried out by heating for 2 hours to obtain a light yellow transparent molded body. Example 19 The polymethylmethacrylate resin molded body was replaced with a polycarbonate resin molded body having a polymethylmethacrylate resin as a mutual dissolution protective layer, and otherwise the Example 10
After injecting the monomer containing the radical initiator prepared by the same formulation as in Example 2 into the template having the same content as shown in, the mixture was placed in a hot-air stove and polymerized by heating at 60 to 170 ° C. for 3 hours. Thus, a colorless and transparent molded body was obtained. Example 20 A monomer containing a radical initiator prepared by the same formulation as in Example 4 was poured into a mold having the same content as shown in Example 19, which was placed in a hot-air stove and further heated at 55 ° C. for 1 hour. ℃
Polymerization was carried out for 2 hours to obtain a colorless and transparent molded body. Example 21 A monomer containing a radical initiator prepared by the same formulation as in Example 6 was poured into a mold having the same contents as shown in Example 19, which was placed in a hot air stove and further heated at 60 ° C. for 1 hour and further 160 ℃
Polymerization was carried out for 2 hours to obtain a colorless and transparent molded body. Example 22 A monomer containing a radical initiator prepared by the same formulation as in Example 7 was poured into a mold having the same content as shown in Example 19, which was placed in a hot stove and heated to 60 ° C to 180 ° C. Polymerization was carried out by heating for 2 hours to obtain a light yellow transparent molded body. Example 23 3-isopropenyl-α, α-dimethylbenzylisocyanate To 223 parts, dibutyltin dilaurate 0.56 parts was added, and while heating the internal temperature to 60 ° C., 144 parts of hydroxyethyl methacrylate was gradually added, A urethanization reaction was performed to obtain a monomer represented by the following structural formula (Formula 44).

[0082]

[Chemical 44] To this, 33 parts of ethylene glycol bis (3-mercaptopropionate) was added, and 1.2 parts of t-butylperoxy-2-ethylhexanoate was further added to this, and mixed well and defoamed to obtain a uniform solution. And This liquid was poured into a mold having the same contents as shown in Example 1, and the temperature was raised from 70 ° C. to 150 ° C. over 2 hours in a hot air oven for polymerization to carry out polymerization. Then, it was cooled and released from the mold to obtain a transparent resin plate having a smooth surface. Example 24 To 201 parts of 4-isopropenyl-α, α-dimethylbenzyl isocyanate, 0.5 part of dibutyltin dilaurate was added, and 214 parts of glycerol-1-acrylate-3-methacrylate was added while heating the internal temperature to 60 ° C. Was gradually added to carry out a urethanization reaction to obtain a monomer represented by the following structural formula (Formula 45).

[0083]

[Chemical formula 45] To this, 19 parts of 1,6-hexanedithiol was added, and t-butylperoxy-2-ethylhexanoate 2.1
Parts were added, mixed well and defoamed to obtain a uniform liquid. This liquid was poured into a mold having the same contents as in Example 1, and then polymerization was carried out under the same conditions as in Example 23 to obtain a transparent resin plate having a smooth surface. Example 25 To 134 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 0.03 part of dibutyltin dilaurate was added, and 77 parts of 2-hydroxyethyl acrylate was gradually added while heating the internal temperature to 60 ° C. Then, a urethanization reaction was performed to obtain a monomer represented by the following structural formula (Formula 46).

[0084]

[Chemical formula 46] To this, 41 parts of pentaerythritol tetrakis (3-mercaptopropionate), 94 parts of tris (acryloyloxyethyl) isocyanurate, and 35 parts of styrene were added,
Further, 1.9 parts of t-butylperoxy-2-ethylhexanoate was added thereto, mixed well and defoamed to obtain a uniform liquid. This liquid was poured into a mold having the same contents as in Example 1, and then polymerization was performed under the same conditions as in Example 23 to obtain a transparent resin plate. Example 26 To 167 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 0.4 part of dibutyltin dilaurate was added, and 27 parts of ethylene glycol was gradually added while heating the internal temperature to 60 ° C. to obtain urethane. Was carried out to obtain a monomer represented by the following structural formula (Formula 47).

[0085]

[Chemical 47] To this, 51 parts of pentaerythritol tetrakis (3-mercaptopropionate) and 146 parts of pentaerythritol tetraacrylate were added, and 1.9 parts of t-butylperoxy-2-ethylhexanoate was further added to this, and mixed well and defoamed. To obtain a uniform liquid. This solution was poured into a mold having the same contents as shown in Example 1, and then Example 23 was used.
Polymerization was carried out under the same conditions as those shown in 1. to obtain a resin plate having a transparent surface. Example 27 To 120 parts of 4-isopropenyl-α, α-dimethylbenzyl isocyanate, 0.3 part of dibutyltin dilaurate was added, and while heating the internal temperature to 60 ° C., 24 parts of methanol was gradually added to carry out the urethanization reaction. After that, excess methanol was distilled off to obtain a monomer represented by the following structural formula (Formula 48).

[0086]

[Chemical 48] To this, 54 parts of diethylene glycol bis (2-mercaptoacetate) and 201 parts of trimethylolpropane trimethacrylate were added, and further 2.0 parts of t-butylperoxy-2-ethylhexanoate was added thereto and mixed well,
It was defoamed to obtain a uniform liquid. This liquid was poured into a mold having the same contents as in Example 1 and polymerization was carried out under the same conditions as in Example 23 to obtain a transparent molded body.

Example 28 A monomer containing a radical initiator prepared by the same formulation as shown in Example 23 was injected into a mold having the same contents as shown in Example 10, and the mold was placed in a hot stove to carry out the operation. Polymerization was carried out under the same conditions as shown in Example 23 to obtain a transparent molded body. Example 29 A monomer containing a radical initiator prepared by the same formulation as shown in Example 24 was poured into a mold having the same contents as shown in Example 10, and this was placed in a hot stove to give Example 24. Polymerization was performed under the same conditions as shown to obtain a transparent molded body. Example 30 A monomer containing a radical initiator prepared by the same formulation as shown in Example 25 was poured into a mold having the same contents as shown in Example 10, and this was placed in a hot-blast stove to give Example 25. Polymerization was performed under the same conditions as shown to obtain a transparent molded body. Example 31 A monomer containing a radical initiator prepared by the same formulation as shown in Example 26 was poured into a mold having the same content as shown in Example 10, and this was placed in a hot stove to give Example 26. Polymerization was performed under the same conditions as shown to obtain a transparent molded body. Example 32 85 parts of monomer prepared with the same formulation as shown in Example 23 and monomer prepared with the same formulation as shown in Example 26
To 120 parts, add 47 parts of pentaerythritol tetrakis (3-mercaptopropionate) and 136 parts of pentaerythritol tetraacrylate, and add 2.5 parts of t-butylperoxy-2-ethylhexanoate to this and mix well. , Then degassed. This monomer was poured into a mold having the same contents as shown in Example 1 except that the polymethylmethacrylate resin molded body was replaced with a polycarbonate resin molded body, and this was placed in a hot air stove and heated to 70 ° C to 170 ° C. Polymerization was performed by heating for 2 hours to obtain a transparent molded body. Example 33 A radical initiator-containing monomer prepared by the same formulation as shown in Example 5 was used in the same mold as that shown in Example 10 except that the polymethylmethacrylate resin molded body was replaced with the polycarbonate resin molded body. After injection, this was placed in a hot air oven and polymerization was carried out under the same conditions as shown in Example 1 to obtain a transparent molded body.

Example 34 A radical initiator-containing monomer prepared by the same formulation as shown in Example 23 was poured into a mold having the same contents as shown in Example 15, which was placed in a hot-blast stove to carry out the operation. Polymerization was carried out under the same conditions as shown in Example 23 to obtain a transparent molded body. Example 35 A monomer containing a radical initiator prepared by the same formulation as shown in Example 25 was poured into a mold having the same contents as shown in Example 15, which was placed in a hot stove, and then added to Example 25. Polymerization was carried out under the same conditions as shown to obtain a transparent molded body. Example 36 A monomer having a radical initiator and prepared in the same formulation as shown in Example 27 was poured into a mold having the same contents as shown in Example 15, and this was placed in a hot stove to give Example 27. Polymerization was carried out under the same conditions as shown to obtain a transparent molded body. Example 37 A monomer containing a radical initiator prepared by the same formulation as shown in Example 24 was poured into a mold having the same content as shown in Example 19, which was placed in a hot air stove, and then added to Example 24. Polymerization was carried out under the same conditions as shown to obtain a transparent molded body. Example 38 A monomer having a radical initiator prepared in the same formulation as shown in Example 26 was poured into a mold having the same contents as shown in Example 19, which was placed in a hot stove to give Example 26. Polymerization was carried out under the same conditions as shown to obtain a transparent molded body. Example 39 To 402 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 1 part of dibutyltin dilaurate and 200 parts of methanol were mixed, and the reaction was carried out by stirring for 30 minutes under reflux of methanol. After completion of the reaction, methanol was distilled off and the residue was further purified by a chromatographic method to obtain 396 parts of a colorless liquid monomer represented by the following structural formula (Formula 49).

[0089]

[Chemical 49] To 233.4 parts of the thus obtained monomer was added 141.2 parts of tris (acryloyloxyethyl) isocyanurate and mixed well, then 3.8 parts of benzoyl peroxide was added and mixed and degassed. It was poured into a polymerization mold having the same contents as shown in 1 above, placed in a hot-air stove, heated in the polymerization hot-air stove from 70 ° C to 150 ° C over 1.5 hours, and then polymerized. It was cooled and released from the mold to obtain a transparent resin plate having a smooth surface.

Example 40 35.7 parts of ethylene glycol, 173 parts of toluene, 3-isopropenyl-α, α-dimethylbenzyl isocyanate
231.7 parts, 1.2 parts dibutyltin dilaurate are mixed,
The reaction was carried out by stirring for 1 hour while maintaining the reaction liquid temperature at 80 ° C. After the reaction was completed, the reaction solution was concentrated. The concentrated solution was purified by a chromatographic method to obtain 1,2-bis [N-
232 parts of (3-isopropenyl-α, α-dimethylbenzyl) carbamoyloxy] ethane were obtained. And, to this product, pentaerythritol tetraacrylate 176
Part, and 3 parts of benzoyl peroxide were added, mixed well, degassed and homogenized, poured into a mold having the same contents as shown in Example 1, and heated at 70 ° C. to 150 ° C. in a hot air oven for polymerization.
The temperature was raised to 1.5 ° C. over 1.5 hours, polymerization was performed, and then the mixture was cooled and released from the mold to obtain a transparent resin plate having a smooth surface. Example 41 Ethylene glycol 62 parts, toluene 300 parts, 4-isopropenyl-α, α-dimethylbenzyl isocyanate 4
03 parts and 2 parts of dibutyltin dilaurate were mixed, and the reaction was carried out by stirring for 1 hour while maintaining the reaction liquid temperature at 80 ° C. After the reaction was completed, the reaction solution was concentrated. The concentrated solution was purified by a chromatographic method to obtain 1,2-bis [N- (4-
412 parts of isopropenyl-α, α-dimethylbenzyl) carbamoyloxy] ethane were obtained. And this product
Pentaerythritol tetraacrylate 176 in 232 parts
Parts, and 3 parts of benzoyl peroxide were added, mixed well, degassed and homogenized into a mold having the same contents as shown in Example 1 to carry out polymerization under the same conditions as in Example 38, A transparent molded body was obtained. Example 42 The procedure of Example 40 was repeated, except that 35.7 parts of ethylene glycol in Example 40 was replaced with 61.0 parts of diethylene glycol, and bis [2- {N- (3-isopropenyl-α, α-dimethyl) was obtained as a colorless transparent liquid. 272 parts of benzyl) carbamoyloxy} ethyl] ether were obtained. Then, 237.8 parts of trimethylolpropane trimethacrylate and 2.1 parts of benzoyl peroxide were added to 177.8 parts of this product, mixed well, degassed, and a uniform solution was poured into a mold having the same contents as shown in Example 10. In a hot air oven for polymerization
The temperature was raised from 70 ° C to 150 ° C over 1.5 hours to obtain a transparent resin plate with a smooth surface.

Example 43 Example 40 was repeated except that 35.7 parts of ethylene glycol of Example 40 was replaced with 112.9 parts of tricyclo [5,2,1,0 ^2,8 ] decane-4,8-dimethanol. 321.9 parts of 4,8-bis [N- (3-isopropenyl-α, α-dimethylbenzyl) carbamoyloxymethyl] tricyclo [5,2,1,0 ^2,8 ] decane in the form of a colorless transparent liquid was obtained. Then, to 239.2 parts of this product, 160 parts of ethyl acrylate and 2.4 parts of benzoyl peroxide were added and mixed well, followed by defoaming to obtain a uniform solution, which was then poured into a mold having the same contents as in Example 11 to carry out polymerization. From 70 ℃ to 150 ℃ in a hot stove
The temperature was raised over 1.5 hours, polymerization was carried out, then the mixture was cooled and released from the mold to obtain a transparent resin plate having a smooth surface. Example 44 Glycerol 42.7 parts, toluene 210 parts, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 282.1
And 1.4 parts of dibutyltin dilaurate were mixed, and the reaction was carried out by stirring for 1 hour while maintaining the reaction liquid temperature at 90 ° C. After the reaction was completed, the reaction solution was concentrated. The concentrated solution was purified by a chromatographic method to obtain 1,2,3-tris [N-
296.3 parts of (3-isopropenyl-α, α-dimethylbenzyl) carbamoyloxy] propane were obtained. 221.8 parts of this product contain pentaerythritol tetraacrylate
184.8 parts and 2.1 parts of benzoyl peroxide were added, mixed well, degassed and homogenized, poured into a mold having the same contents as shown in Example 10, and heated in a hot air oven for polymerization.
The temperature was raised from ℃ to 150 ℃ over 1.5 hours, polymerization was carried out, then cooled and released from the mold to obtain a transparent resin plate having a smooth surface. Example 45 A monomer containing a radical initiator prepared by the same formulation as shown in Example 44 was injected into a mold having the same contents as shown in Example 13, and polymerization was carried out under the same conditions as shown in Example 43. As a result, a transparent molded body was obtained.

Example 46 A radical initiator-containing monomer prepared by the same formulation as shown in Example 39 was poured into a mold having the same contents as shown in Example 10, and the same conditions as shown in Example 39 were used. Polymerization was performed to obtain a transparent molded body. Example 47 A monomer containing a radical initiator prepared by the same formulation as shown in Example 40 was poured into a mold having the same contents as shown in Example 1, and polymerized under the same conditions as shown in Example 40. , A transparent molded body was obtained. Example 48 A monomer containing a radical initiator prepared by the same formulation as shown in Example 43 was poured into a mold having the same contents as shown in Example 19, and polymerized under the same conditions as shown in Example 43. , A transparent molded body was obtained. Example 49 A monomer containing a radical initiator prepared by the same formulation as shown in Example 43 was poured into a mold having the same contents as shown in Example 13, and polymerized under the same conditions as shown in Example 43. , A transparent molded body was obtained.

Example 50 A monomer containing a radical initiator prepared by the same formulation as shown in Example 43 was poured into a mold having the same contents as shown in Example 15, and the same conditions as shown in Example 43 were used. Polymerization gave a transparent molded body. Example 51 4-isopropenylphenol 386.6 parts, benzene 2300
And 378.9 parts of triethylamine were mixed, 300 parts of acrylic acid chloride was added dropwise over 60 minutes while cooling with ice, and the mixture was stirred at room temperature for 4 hours for reaction. After completion of the reaction, the product was purified by column chromatography to obtain 450 parts of a colorless liquid ester compound represented by the following structural formula (Formula 50).

[0094]

[Chemical 50] Benzoyl peroxide was added to 400 parts of this ester compound.
After adding 4.1 parts and mixing and defoaming, this liquid was poured into a mold having the same contents as shown in Example 1, and the mixture was heated from 60 ° C. to 160 ° C. for 2 hours in a hot air oven for polymerization. After the temperature was raised and polymerization was carried out, it was cooled and released from the mold to obtain a transparent resin plate having a smooth surface and slightly yellowish color. Example 52 375 parts 3-isopropenylphenol, benzene 2500
And 375 parts of triethylamine were mixed, 350 parts of methacrylic acid chloride was added dropwise over 60 minutes while cooling with ice, and the reaction was carried out by stirring at room temperature for 4 hours. After completion of the reaction, the product was purified by column chromatography to obtain 400 parts of a colorless liquid ester compound represented by the following structural formula (Formula 51).

[0095]

[Chemical 51] Benzoyl peroxide was added to 400 parts of this ester compound.
After adding 2.5 parts and mixing and defoaming, this solution was poured into a mold having the same contents as shown in Example 1 and heated in a hot air oven for polymerization from 60 ° C to 170 ° C over 2 hours. The temperature was raised, the polymerization was carried out, the system was cooled, and the mold was released from the mold to obtain a transparent resin plate having a smooth surface. Example 53 402.0 parts of 4-isopropenylphenol is dissolved in 80% 20% aqueous sodium hydroxide solution and refluxed. 2- here
448.4 parts of bromoethal is added dropwise, and after completion of the addition, the mixture is reacted under reflux for 2 hours with stirring. When the reaction is completed and left to stand, it is separated into two layers, so the oil layer is separated and washed with hot water. The oil layer was dehydrated, filtered, and distilled under reduced pressure to obtain 380.0 parts of a colorless transparent liquid ether product. 380 parts of this ether compound was mixed with 1900 parts of benzene and 275.7 parts of triethylamine, and 218.6 parts of acrylic acid chloride was added dropwise over 60 minutes while cooling with ice.
The reaction was carried out by stirring at room temperature for 4 hours. After completion of the reaction, the product was purified by column chromatography,
387.6 parts of a colorless liquid ester compound represented by 2) was obtained.

[0096]

[Chemical 52] To 380.0 parts of this ester compound, 3.8 parts of benzoyl peroxide was added, mixed and defoamed, and then this solution was poured into a mold having the same contents as shown in Example 1 and heated in a hot air oven for polymerization to 60 The temperature was raised from 0 ° C. to 170 ° C. over 2 hours, polymerization was carried out, followed by cooling and releasing from the mold to obtain a transparent resin plate having a smooth surface. Example 54 182.0 parts of propion oxide, 348.4 parts of 3-isopropenylphenol, 5.2 parts of sodium hydroxide, and 650 parts of ethanol were mixed, and the mixture was heated and stirred under reflux to carry out a ring-opening reaction. After the completion of the reaction, the reaction solution was concentrated and purified by extraction and recrystallization to obtain 421.2 parts of a ring-opened product of propylene oxide with 3-isopropenylphenol. 378.7 parts of this ring-opened product was mixed with 1800 parts of benzene and 258.8 parts of triethylamine, 204.5 parts of acrylic acid chloride was added dropwise over 60 minutes while cooling with ice, and the reaction was carried out at room temperature for 4 hours with stirring. After completion of the reaction, the product was purified by column chromatography to obtain 376.2 parts of a colorless liquid ester compound represented by the following structural formula (Formula 53).

[0097]

[Chemical 53] To 370.0 parts of this ester compound, 3.8 parts of benzoyl peroxide was added, mixed and defoamed, and then this solution was poured into a mold having the same contents as shown in Example 11, and the mixture was heated in a hot air oven for polymerization to 60%. Temperature rise from ℃ to 160 ℃ over 2 hours,
After the polymerization, it was cooled and released from the mold to obtain a transparent resin plate having a smooth surface. Example 55 3-Isopropenylphenol 210.0 parts to 2-isocyanatoethyl methacrylate 242.9 parts, toluene 140
And 2.1 parts of dibutyltin dilaurate were added, and the internal temperature was 50
The reaction was carried out by heating and stirring so as to reach ℃. After the reaction was completed, the reaction solution was concentrated. The concentrated liquid was purified by a chromatographic method to obtain 394.1 parts of a colorless liquid urethane compound represented by the following structural formula (Formula 54).

[0098]

[Chemical 54] To 385.0 parts of this urethane compound, 4.2 parts of benzoyl peroxide was added, mixed and defoamed, and then this solution was poured into a mold having the same contents as shown in Example 11, and the mixture was heated in a hot air oven for polymerization to 60%. Temperature rise from ℃ to 170 ℃ over 2 hours,
After the polymerization, the mixture was cooled and released from the mold to obtain a transparent resin plate having a smooth surface and a slight yellowish tint.

Example 56 To 242.4 parts of the ester compound of Example 53, 135.6 parts of trimethylolpropane trimethacrylate and 3.6 parts of benzoyl peroxide were added, mixed and defoamed, and this solution was the same as that shown in Example 11. It is poured into the mold of the contents, heated in a hot air oven for polymerization from 60 ° C to 170 ° C over 2 hours, polymerized, cooled, and then released from the mold to make the surface smooth and transparent. A resin plate was obtained. Example 57 A monomer containing a radical initiator prepared by the same formulation as shown in Example 51 was poured into a mold having the same contents as shown in Example 10, and polymerized under the same conditions as shown in Example 51. A light yellow transparent molded body was obtained. Example 58 A monomer containing a radical initiator prepared by the same formulation as shown in Example 52 was poured into a mold having the same contents as shown in Example 10, and polymerized under the same conditions as shown in Example 52. A colorless and transparent molded body was obtained. Example 59 A monomer containing a radical initiator prepared in the same formulation as shown in Example 53 was poured into a mold having the same contents as shown in Example 10, and polymerized under the same conditions as shown in Example 53. A colorless and transparent molded body was obtained. Example 60 A monomer containing a radical initiator prepared by the same formulation as shown in Example 54 was poured into a mold having the same contents as shown in Example 13, and polymerized under the same conditions as shown in Example 54. A transparent molded body was obtained. Example 61 A radical initiator-containing monomer prepared by the same formulation as in Example 55 was poured into a mold having the same content as in Example 13, and polymerized under the same conditions as in Example 55. A light yellow transparent molded body was obtained.

Example 62 A monomer containing a radical initiator prepared by the same formulation as shown in Example 56 was poured into a mold having the same contents as shown in Example 13, and the same conditions as shown in Example 56 were used. Polymerization was performed to obtain a colorless and transparent molded body. Example 63 A monomer containing a radical initiator prepared by the same formulation as shown in Example 51 was poured into a mold having the same contents as shown in Example 15, and polymerized under the same conditions as shown in Example 51. A light yellow transparent molded body was obtained. Example 64 A radical initiator-containing monomer prepared in the same formulation as in Example 52 was poured into a mold having the same content as in Example 15, and polymerized under the same conditions as in Example 52. A colorless and transparent molded body was obtained. Example 65 A monomer containing a radical initiator prepared by the same formulation as shown in Example 53 was poured into a mold having the same contents as shown in Example 15, and polymerized under the same conditions as shown in Example 53. A colorless and transparent molded body was obtained. Example 66 A radical initiator-containing monomer prepared by the same formulation as shown in Example 51 was poured into a mold having the same contents as shown in Example 19, and polymerized under the same conditions as shown in Example 51. A light yellow transparent molded body was obtained.

Example 67 A monomer containing a radical initiator prepared by the same formulation as shown in Example 52 was poured into a mold having the same contents as shown in Example 19, and the same conditions as shown in Example 52 were used. Polymerization was performed to obtain a colorless and transparent molded body. Example 68 A radical initiator-containing monomer prepared by the same formulation as shown in Example 53 was poured into a mold having the same contents as shown in Example 19, and polymerized under the same conditions as shown in Example 53. A colorless and transparent molded body was obtained. Example 69 3-isopropenylphenol 150.2 parts, isophorone diisocyanate 124.4 parts, dibutyltin dilaurate
1.1 parts of toluene and 112 parts of toluene were mixed, and the reaction was carried out by stirring for 2 hours while maintaining the reaction liquid temperature at 70 ° C. After the reaction was completed, the reaction solution was concentrated. The concentrated liquid was purified by a chromatographic method to obtain 250.0 parts of a colorless transparent liquid monomer represented by the following structural formula (Formula 55).

[0102]

[Chemical 55] To 245.4 parts of this monomer, 176.2 parts of pentaerythritol tetraacrylate was added and mixed well, and then 4.8 parts of benzoyl peroxide was added and mixed and defoamed. In a hot air oven for polymerization, the temperature was raised from 70 ° C to 170 ° C over 1.5 hours, the polymerization was performed and then cooled, and the resin was released from the mold to form a transparent and transparent resin plate. Obtained. Example 70 3-isopropenylphenol 240.7 parts, water 4300 parts,
Mix and dissolve 86.2 parts of sodium hydroxide. With vigorous stirring, 3500 parts of a solution of 163.5 parts of adipic acid chloride in methylene chloride was added dropwise, and after completion of the addition, the reaction was carried out at room temperature for 3 hours and under reflux of methylene chloride for 2 hours. The methylene chloride layer was washed with a 5% aqueous sodium hydroxide solution, the organic layer was separated, dried, and then the organic layer was concentrated to recrystallize the resulting crystal to recrystallize from ethanol to give a white solid represented by the following structural formula: 56)
251.5 parts of the above monomer was obtained.

[0103]

[Chemical 56] Divinylbenzene (131.6 parts) was added to this monomer (245.7 parts) and mixed well, and then benzoyl peroxide (3.5 parts) was added to perform mixing and defoaming. Polymerization was carried out under the same conditions as shown in Example 69 to obtain a transparent molded body. Example 71 210.1 parts of 4-isopropenylphenol is mixed with ethanol.
It is dissolved in a mixed solution of 470 parts, water 78 parts and sodium hydroxide 62.7 parts, and heated to reflux. 266.6 parts of iodoethane is added dropwise thereto, and the mixture is reacted under reflux for 3 hours. After completion of the reaction, the solvent is distilled off and the formed precipitate is filtered off. The solution was distilled under reduced pressure to obtain 191.3 parts of a colorless transparent liquid monomer represented by the following structural formula (Formula 57).

[0104]

[Chemical 57] Then, 182.6 parts of this product was added with 202.6 parts of pentaerythritol tetraacrylate and mixed well, then 2.1 parts of benzoyl peroxide was added and mixed and defoamed, and this liquid was used as a template having the same content as that shown in Example 11. Then, the mixture was injected into the flask and polymerized under the same conditions as in Example 69 to obtain a transparent molded body.

Example 72 A monomer containing a radical initiator prepared by the same formulation as shown in Example 69 was poured into a mold having the same contents as shown in Example 13, and the same conditions as shown in Example 69 were used. Polymerization gave a transparent molded body. Example 73 A monomer containing a radical initiator prepared by the same formulation as shown in Example 70 was poured into a mold having the same contents as shown in Example 13, and polymerized under the same conditions as shown in Example 69. A transparent molded body was obtained. Example 74 A monomer containing a radical initiator prepared by the same formulation as shown in Example 71 was poured into a mold having the same contents as shown in Example 10, and polymerized under the same conditions as shown in Example 69. A transparent molded body was obtained. Example 75 A monomer containing a radical initiator prepared by the same formulation as shown in Example 71 was poured into a mold having the same contents as shown in Example 15, and polymerized under the same conditions as shown in Example 69. A transparent molded body was obtained. Example 76 A monomer containing a radical initiator prepared by the same formulation as shown in Example 71 was poured into a mold having the same contents as shown in Example 19, and polymerized under the same conditions as shown in Example 69. A transparent molded body was obtained.

Example 77 4-isopropenylphenol 123.3 parts, toluene 460
Part, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 184.9 parts and dibutyltin dilaurate 2.8
The parts were mixed, and the reaction was carried out by stirring for 3 hours while maintaining the reaction liquid temperature at 100 ° C. After the reaction was completed, the reaction solution was concentrated. The concentrated solution was purified by a chromatographic method to obtain a white solid [N-
(3-isopropenyl-α, α-dimethylbenzyl)]
192.3 parts of (4-isopropenylphenyl) carbamate was obtained. To 177.5 parts of this product, 175.0 parts of neopentyl glycol diacrylate and 1.0 part of benzoyl peroxide were added, mixed well, and degassed to obtain a uniform solution, which was poured into a mold having the same contents as shown in Example 11. Then, the temperature was raised from 70 ° C. to 170 ° C. over 1.5 hours in a hot air oven for polymerization, polymerization was carried out, then the system was cooled and released from the mold to obtain a transparent resin plate having a smooth surface. Example 78 A colorless liquid [N- (3-isopropenyl-α, α-dimethyl] was prepared in the same manner as in Example 77 except that 105.6 parts of 4-isopropenylphenol of Example 77 was replaced with 105.6 parts of 3-isopropenylphenol. Benzyl)] (3-isopropenylphenyl) carbamate (190.0 parts) was obtained. To this product (187.5 parts) were added pentaerythritol tetraacrylate (197.0 parts) and benzoyl peroxide (1.25 parts), and the mixture was thoroughly mixed and degassed to obtain a uniform solution. Then, the temperature was raised from 70 ° C. to 170 ° C. over 1.5 hours in a hot air oven for polymerization, the polymerization was carried out, then the system was cooled and released from the mold to obtain a transparent resin plate having a smooth surface.

Example 79 2- (3-isopropenylphenoxy) ethanol 98.1
Parts, 165 parts of toluene, 110.7 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 1.1 parts of dibutyltin dilaurate were mixed, and the reaction was carried out by stirring for 2 hours while maintaining the reaction liquid temperature at 80 ° C. After the reaction was completed, the reaction solution was concentrated. The concentrated liquid was purified by a chromatographic method to obtain 200.0 parts of [N- (3-isopropenyl-α, α-dimethylbenzyl)] [2- (3-isopropenylphenoxy) ethyl] carbamate as a colorless transparent liquid. This product
196.2 parts pentaerythritol tetraacrylate 1
82.0 parts and 1.2 parts of benzoyl peroxide were added and mixed well, and the solution which had been degassed and homogenized was poured into a mold having the same contents as shown in Example 11 to carry out polymerization of the same formulation as shown in Example 77. Then, a transparent molded body was obtained. Example 80 [N- (3-isopropenyl-α, α-dimethylbenzyl)] [2- (3-isopropenylphenoxy) ethyl] carbamate obtained in the same manner as in Example 79 221.6
151.9 parts of divinylbenzene and 1.1 parts of benzoyl peroxide were added to the above parts, mixed well, and defoamed to obtain a uniform liquid, which was poured into a mold having the same contents as shown in Example 11 to give the solution shown in Example 77. Polymerization was performed under the same conditions to obtain a colorless and transparent molded body. Example 81 2- (3-isopropenylphenoxy) -1-methylethanol 117.4 parts, toluene 183.5 parts, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 12
2.9 parts and dibutyltin dilaurate 0.66 parts were mixed, and the reaction was carried out by stirring for 2 hours while maintaining the reaction liquid temperature at 80 ° C. After the reaction was completed, the reaction solution was concentrated. The concentrated solution was purified by a chromatographic method to obtain a colorless transparent liquid [N- (3-isopropenyl-α, α-dimethylbenzyl)] [2- (3-
222.0 parts of isopropenylphenoxy) -1-methylethyl] carbamate was obtained. To 216.5 parts of this product, 163.3 parts of trimethylolpropane trimethacrylate and 0.99 parts of benzoyl peroxide were added, mixed well, and defoamed to obtain a uniform solution, which was poured into a mold having the same contents as shown in Example 11. Polymerization was performed under the same conditions as in Example 77 to obtain a colorless and transparent molded body. Example 82 A monomer containing a radical initiator prepared by the same formulation as shown in Example 77 was poured into a mold having the same contents as shown in Example 10, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 83 A monomer containing a radical initiator prepared by the same formulation as shown in Example 78 was poured into a mold having the same contents as shown in Example 10, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 84 A radical initiator-containing monomer prepared by the same formulation as in Example 79 was poured into a mold having the same content as in Example 13, and polymerized under the same conditions as in Example 77. , A transparent molded body was obtained. Example 85 A monomer containing a radical initiator prepared by the same formulation as shown in Example 80 was poured into a mold having the same contents as shown in Example 13, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 86 A monomer containing a radical initiator prepared by the same formulation as shown in Example 81 was poured into a mold having the same contents as shown in Example 13, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 87 A monomer containing a radical initiator prepared in the same formulation as shown in Example 79 was poured into a mold having the same contents as shown in Example 15, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained.

Example 88 A monomer having a radical initiator prepared in the same formulation as shown in Example 80 was poured into a mold having the same contents as shown in Example 15, and the same conditions as shown in Example 77 were used. Polymerization gave a transparent molded body. Example 89 A monomer containing a radical initiator prepared by the same formulation as shown in Example 81 was poured into a mold having the same contents as shown in Example 15, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 90 A monomer containing a radical initiator prepared by the same formulation as shown in Example 79 was poured into a mold having the same contents as shown in Example 19, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 91 A monomer containing a radical initiator prepared by the same formulation as shown in Example 80 was poured into a mold having the same content as shown in Example 19, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 92 3-isopropenyl-α, α-dimethylbenzyl isocyanate (241.4 parts) and dibutyltin dilaurate (0.24 parts) were added, and diethylene glycol monomethacrylate (209.0 parts) was gradually added while heating so that the internal temperature was 40 ° C. I went. After completion of the reaction, purification by column chromatography was performed to obtain 391.9 parts of a colorless liquid monomer represented by the following structural formula (Formula 58).

[0109]

[Chemical 58] To 370 parts of this product, 0.4 part of t-butyl-peroxy-2-ethylhexanoate was added, and then the monomer was polymerized under the same template and the same conditions as those shown in Example 1. Example 93 Polycarbonate resin molding having a radical initiator-containing monomer prepared in the same formulation as in Example 7 and a polymethylmethacrylate resin molding, and an acrylic photocurable resin as a mutual dissolution protective layer [Sekisui Fine Chemical Co., Ltd. 25 parts of a photosensitizer (trade name: Photorec RW-101 / B) is added to 2500 parts of water-soluble photoresist (trade name: Photorec RW-101 / A) manufactured by Co., Ltd. (10% resin content). In addition, immerse the transparent resin molding in the dissolved solution,
After removing the solvent, the solvent was removed, and then the light was irradiated with a mercury lamp (50 to 80 mj / cm ² ) to cure to obtain a molded body], and otherwise, in the polymerization mold of Example 1 aspect. After injection, the mold was placed in a hot air oven and polymerization was carried out under the same conditions as in Example 7.

Example 94 Monomer 40 prepared with the same formulation as shown in Example 7.
To 0.0 parts, 55.4 parts of pentaerythritol tetrakis (3-mercaptopropionate) was added and mixed well. 0.46 parts of t-butylperoxy-2-ethylhexanoate was added to this mixture as a radical initiator, and the mixture was thoroughly stirred and then degassed. Then, this monomer was injected into a mold having the same form as that shown in Example 93, and polymerization was carried out under the same conditions as in Example 7. Example 95 3-Isopropenyl-α, α-dimethylbenzyl isocyanate (150.0 parts) and ethylene glycol (15.3 parts) were mixed with dibutyltin dilaurate (0.0) as a reaction catalyst.
8 parts was added, and the urethanization reaction was carried out for 1 hour while maintaining the internal temperature at 40 ° C. Then, 92.3 parts of diethylene glycol monomethacrylate was gradually added to this reaction solution,
The urethane reaction was carried out for 2 hours while maintaining the internal temperature at 50 ° C. Then, 131.3 parts of pentaerythritol tetraacrylate was further added to this reaction solution and mixed well, then, to this acrylate mixture of urethane compound,
As a radical initiator, 0.39 part of t-butylperoxy-2-ethylhexanoate was added, and after thoroughly stirring, defoaming was performed. Then, this monomer was added to Example 9
It poured into the mold of the same aspect as shown in 3, and the polymerization of the same conditions as Example 7 was performed after that. Example 96 A radical initiator-containing monomer prepared according to the same formulation as in Example 95 was added to a polymethylmethacrylate resin molded body,
After changing to a polycarbonate resin molded body having a polymethylmethacrylate resin as a mutual dissolution protection layer, and injecting it into a mold having the same contents as shown in Example 1 other than that, it was placed in a hot air stove and heated to 60 to 170 ° C. Polymerization was carried out for 3 hours by heating at elevated temperature.

Example 97 A radical initiator-containing monomer prepared in the same manner as in Example 94 was used, and a polymethylmethacrylate resin molded product was used.
After changing to a polycarbonate resin molded body having a polymethylmethacrylate resin as a mutual dissolution protection layer, and injecting it into a mold having the same contents as shown in Example 1 other than that, it was placed in a hot air stove and heated to 60 to 170 ° C. Polymerization was carried out for 3 hours by heating at elevated temperature. Example 98 The same content as shown in Example 1 except that the radical initiator-containing monomer prepared by the same formulation shown in Example 32 was replaced with a polyvinyl chloride resin molded body. It was poured into a mold, placed in a hot air oven, and polymerized under the same conditions as shown in Example 32 to obtain a transparent molded body. Example 99 The same content as shown in Example 10 except that the radical initiator-containing monomer prepared by the same formulation shown in Example 32 was replaced with a polyvinyl chloride resin molded body instead of the polymethylmethacrylate resin molded body. It was poured into a mold, placed in a hot air oven, and polymerized under the same conditions as shown in Example 32 to obtain a transparent molded body. Example 100 A polymethylmethacrylate resin molded body was replaced with a polyvinyl chloride resin molded body by using a monomer containing a radical initiator prepared in the same formulation as in Example 40, and Example 4 was used.
Polymerization in the same manner as shown in 0 was performed to obtain a transparent molded body. Example 101 A monomer containing a radical initiator prepared by the same formulation as in Example 53 was replaced with a polyvinyl chloride resin molded product in place of the polymethacrylate resin molded product, and otherwise the same as in Example 10. Example 5 poured into a mold
Polymerization was carried out under the same conditions as shown in 3 to obtain a colorless and transparent molded body.

Example 102 The same content as shown in Example 1 was used, except that the polymethylmethacrylate resin molding was replaced with the epoxy resin molding for the monomer containing the radical initiator prepared by the same formulation as in Example 5. Inject it into the mold, set it in the hot stove,
Polymerization was performed for 3 hours by heating from 60 ° C to 170 ° C. Example 103 A radical initiator-containing monomer prepared by the same formulation as shown in Example 51 was poured into a mold having the same contents as shown in Example 102, and polymerized under the same conditions as shown in Example 51. A light yellow transparent molded body was obtained. Example 104 A monomer containing a radical initiator prepared by the same formulation as shown in Example 52 was poured into a mold having the same contents as shown in Example 102, and polymerized under the same conditions as shown in Example 52. A colorless and transparent molded body was obtained. Example 105 A monomer containing a radical initiator prepared by the same formulation as shown in Example 70 was poured into a mold having the same contents as shown in Example 102, and polymerized under the same conditions as shown in Example 69. A transparent molded body was obtained. Example 106 A monomer containing a radical initiator prepared by the same formulation as shown in Example 73 was poured into a mold having the same contents as shown in Example 102, and polymerized under the same conditions as shown in Example 69. A transparent molded body was obtained. Example 107 A monomer containing a radical initiator prepared by the same formulation as shown in Example 77 was poured into a mold having the same contents as shown in Example 102, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 108 Except that a polymethylmethacrylate resin molded body was replaced with a polyester resin molded body using a monomer containing a radical initiator prepared by the same formulation as shown in Example 53,
Polymerization was carried out under the same conditions and conditions as in Example 53 to obtain a colorless and transparent molded product. Example 109 A polymethylmethacrylate resin molded body was replaced with a diallylphthalate resin molded body using a monomer containing a radical initiator prepared by the same formulation as in Example 39,
Polymerization was performed under the same conditions as in Example 39 to obtain a transparent molded body.

Example 110 A polymethylmethacrylate resin molded body was replaced with a polyurethane resin molded body by using a monomer containing a radical initiator prepared by the same formulation as in Example 39, and Example 3 was used.
Polymerization was carried out under the same conditions as shown in 9 to obtain a transparent molded body. Example 111 The same content as shown in Example 51 except that the polymethylmethacrylate resin molded body was replaced with the polyacetal resin molded body by using the monomer containing the radical initiator prepared by the same formulation as shown in Example 51. Polymerization was performed under the same conditions as in the mold to obtain a light yellow transparent molded body. Example 112 Example 1 was repeated, except that the radical initiator-containing monomer prepared by the same formulation as in Example 3 was replaced with an unsaturated polyester resin molded body instead of the polymethylmethacrylate resin molded body.
It was poured into a mold having the same contents as shown in 1 above, placed in a hot-air stove, and polymerized for 3 hours by heating up to 60 ° C to 170 ° C,
A colorless and transparent molded body was obtained. Example 113 The same content as shown in Example 1 except that the polymethylmethacrylate resin molding was replaced by an unsaturated polyester resin molding instead of the monomer containing the radical initiator prepared in the same formulation as in Example 32. It was poured into a mold, placed in a hot air oven, and polymerized under the same conditions as shown in Example 32 to obtain a transparent molded body. Example 114 A monomer having a radical initiator and prepared in the same formulation as in Example 55 was replaced with an unsaturated polyester resin molded body in place of the polymethacrylate resin molded body, and otherwise the same as in Example 10. It was poured into a mold and polymerized under the same conditions as shown in Example 55 to obtain a light yellow transparent molded body.

Example 115 A radical initiator-containing monomer prepared by the same formulation as shown in Example 69 was poured into a mold having the same content as shown in Example 112, and the same conditions as shown in Example 69 were used. Polymerization gave a transparent molded body. Example 116 A monomer containing a radical initiator prepared by the same formulation as shown in Example 71 was poured into a mold having the same contents as shown in Example 112, and polymerized under the same conditions as shown in Example 69. A transparent molded body was obtained. Example 117 A radical initiator-containing monomer prepared in the same formulation as in Example 73 was poured into a mold having the same content as in Example 112, and polymerized under the same conditions as in Example 69. A transparent molded body was obtained. Example 118 A monomer containing a radical initiator prepared by the same formulation as shown in Example 77 was poured into a mold having the same contents as shown in Example 112, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 119 A monomer containing a radical initiator prepared by the same formulation as shown in Example 78 was poured into a mold having the same contents as shown in Example 112, and polymerized under the same conditions as shown in Example 77. , A transparent molded body was obtained. Example 120 A gasket having a thickness of 0.5 mm and a width of 10 mm was arranged, a thickness of 5 mm,
A monomer containing a radical initiator prepared by the same formulation as described in Example 7 was injected into the space of a polymerization mold composed of two flat plate glasses having a side of 400 mm, and the mold was placed in a hot-air stove to 60 ° C. Polymerization was carried out for 3 hours by heating from 1 to 170 ° C. to obtain a high-hardness transparent resin molding having a thickness of 1 mm and a side of about 380 mm. Then, the polymerization of this mode was carried out once again to obtain two molded articles for convenience. Next, an epoxy resin adhesive was applied to both sides of a polymethylmethacrylate resin molded body having a thickness of 3 mm and one side of 380 mm, and the above-mentioned high-hardness transparent resin molded body was adhered to both coated surfaces. And
This integrated product was placed in an autoclave, degassed under reduced pressure at 70 ° C., and then pressurized to 5 Kgf / cm ² ,
It heated at the same temperature for 2 hours. Then, it was cooled and returned to normal pressure to obtain a composite transparent molded body.

Example 121 Example 120 Using a polymerization template of the embodiment 120, a monomer containing a radical initiator prepared by the same formulation as in Example 3 was polymerized to obtain a high hardness transparent resin molding. And
The polymethylmethacrylate resin molded body in Example 120 was replaced with a polycarbonate resin molded body, and the other aspects of Example 120 were laminated to obtain a composite transparent molded body. Example 122 Example 120 Using the polymerization template of the embodiment 120, polymerization of a monomer containing a radical initiator prepared by the same formulation as shown in Example 25 was carried out to obtain a high hardness transparent resin molding. Then, the lamination of Example 120 was carried out to obtain a composite transparent molded body. Example 123 Example 120 Using the polymerization template of the embodiment 120, a monomer containing a radical initiator prepared by the same formulation as in Example 39 was polymerized to obtain a high hardness transparent resin molded body. Then, the lamination of Example 121 was carried out to obtain a composite transparent molded body. Example 124 Using the polymerization template of Example 120, polymerization of a monomer containing a radical initiator prepared by the same formulation as shown in Example 53 was carried out to obtain a high hardness transparent resin molding. Then, the epoxy resin adhesive in Example 120 was replaced with an unsaturated polyester resin molded body, and an autoclave was used.
70 ° C. was changed to 90 ° C., 5 Kgf / cm ² was changed to 8 Kgf / cm ² , and the other aspects of Example 120 were laminated to obtain a composite transparent molded body. Example 125 Example 120 Using the polymerization template of the embodiment 120, polymerization of a monomer containing a radical initiator prepared by the same formulation as shown in Example 56 was carried out to obtain a high hardness transparent resin molding. Then, the polymethylmethacrylate resin molded body of Example 124 was replaced with a polycarbonate resin molded body, and the other aspects of Example 124 were laminated to obtain a composite transparent molded body. Example 126 Example 120 Using the polymerization template of the embodiment 120, a monomer containing a radical initiator prepared by the same formulation as in Example 77 was polymerized to obtain a high hardness transparent resin molded body. Then, the lamination of Example 125 was carried out to obtain a composite transparent molded body.

Example 127 Example 120 Using the polymerization template of the embodiment 120, polymerization of a monomer containing a radical initiator prepared by the same formulation as shown in Example 71 was carried out to obtain a high hardness transparent resin molding. Then, the polymethylmethacrylate resin molded body in Example 124 is replaced with a polyvinyl chloride resin molded body, or the unsaturated polyester resin adhesive is replaced with a polyvinyl chloride resin, and otherwise, the lamination according to the embodiment 124 mode. Then, a composite transparent molded body was obtained. Example 128 Example 120 Using the polymerization template of the embodiment 120, polymerization of a monomer containing a radical initiator prepared by the same formulation as shown in Example 80 was carried out to obtain a high hardness transparent resin molded body. Then, the lamination of Example 127 was carried out to obtain a composite transparent molded body. Example 129 Example 120 Using the polymerization template of the embodiment, polymerization of a monomer containing a radical initiator prepared by the same formulation as shown in Example 70 was carried out to obtain a high hardness transparent resin molded body. Then, the polymethylmethacrylate resin molded body of Example 124 was replaced with a polyurethane resin molded body, and the other aspects of Example 124 were laminated to obtain a composite transparent molded body. Example 130 Example 120 Using the polymerization template of the embodiment, polymerization of a monomer containing a radical initiator prepared by the same formulation as shown in Example 32 was carried out to obtain a high hardness transparent resin molded body. Then, the polymethylmethacrylate resin molded body in Example 120 was replaced with an unsaturated polyester resin molded body, and the other aspects of Example 120 were laminated to obtain a composite transparent molded body. Example 131 Example 120 Using the polymerization template of the embodiment, polymerization of a monomer containing a radical initiator prepared by the same formulation as shown in Example 44 was carried out to obtain a high hardness transparent resin molded body. Then, the lamination of Example 130 was carried out to obtain a composite transparent molded body.

The composite transparent moldings obtained in Examples 1 to 131 were evaluated by the above-mentioned methods, and the results shown in (Table 1) to (Table 22) were obtained.

[0118]

[Table 1]

[0119]

[Table 2]

[0120]

[Table 3]

[0121]

[Table 4]

[0122]

[Table 5]

[0123]

[Table 6]

[0124]

[Table 7]

[0125]

[Table 8]

[0126]

[Table 9]

[0127]

[Table 10]

[0128]

[Table 11]

[0129]

[Table 12]

[0130]

[Table 13]

[0131]

[Table 14]

[0132]

[Table 15]

[0133]

[Table 16]

[0134]

[Table 17]

[0135]

[Table 18]

[0136]

[Table 19]

[0137]

[Table 20]

[0138]

[Table 21]

[0139]

[Table 22]

Comparative Example 1 1.2 parts of benzoyl peroxide was added to 400 parts of diethylene glycol diallyl carbonate, mixed and defoamed, and this solution was poured into the polymerization mold of Example 1 embodiment.
In the hot air stove for polymerization, the temperature rises from 50 ℃ to 170 ℃ for 3 hours.
The polymer was peeled from the glass mold and colored yellow.

It was possible to obtain a resin plate without peeling for the first time by heating and polymerizing from 50 ° C. to 170 ° C. over 8 hours, but the obtained resin had a pencil hardness of 4H.
Met. The impact resistance was 2.0 Kgf · cm / cm ² and the flexural modulus was 252 Kgf / mm ² . Comparative Example 2 Methyl xylylene diisocyanate (112.8 parts) was added to methyl methacrylate (120.0 parts), dibutyltin dilaurate (0.06 parts) was further added, and hydroxyethyl methacrylate (156.6 parts) was gradually added while heating so that the internal temperature was 60 ° C. A viscous methyl methacrylate mixture of urethane compounds in which absorption of isocyanate groups almost disappeared in the absorption spectrum was obtained. Benzoyl peroxide
3.6 parts were added and mixed and degassed, and this liquid was poured into the polymerization mold of Example 11 and poured into a polymerization hot air oven at 45 ° C.
From 3 to 160 ° C over 3 hours while heating and polymerizing,
A rapid polymerization occurred at around 65 ° C, and the polymer separated from the glass mold. Comparative Example 3 Polymerization was carried out in the same manner as in Example 25 without adding pentaerythritol tetrakis (3-mercaptopropionate) in Example 25 to obtain a transparent resin plate having a smooth surface. The pencil hardness was 5H, but the impact resistance was 6.1 kgfcm / cm ² . Comparative Example 4 t-Butylperoxy-2-ethylhexanoate was added as a radical initiator to the monomer prepared by the same formulation as in Example 2 and polymerized by heating from 60 ° C. to 170 ° C. for 3 hours. Then, a transparent resin plate was obtained.

The pencil hardness of this plate was 7H, but the impact resistance was 6.1 Kgf · cm / cm ² . The flexural modulus is 405 kg.
It was f / mm ² . Comparative Example 5 In Example 15, using a polycarbonate resin molded product having no polymethylmethacrylate resin as a mutual dissolution protection layer, polymerization was carried out for 3 hours by heating from 60 ° C to 170 ° C. In the vicinity, the interface between the polycarbonate resin layer and the monomer resin layer shown in Example 15 became opaque.

Example 132 To 100.6 parts of 3-isopropenyl-α, α-dimethylbenzylisocyanate, 0.1 part of dibutyltin dilaurate was added, and diethylene glycol monomethacrylate 87 was added while heating so that the internal temperature became 40 ° C. .1
Parts were gradually added to carry out a urethanization reaction. After completion of the reaction, the product was purified by column chromatography to obtain a colorless liquid monomer 163.3 represented by the following structural formula (Formula 59).
I got a part.

[0144]

[Chemical 59] Example 133 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 132 was added to 10 parts of 4-isopropenyl-α, α-dimethylbenzyl isocyanate.
Similar to Example 132, except that 0.6 part was substituted,
165.4 parts of a colorless liquid monomer represented by the following structural formula (Formula 60) was obtained.

[0145]

[Chemical 60] Example 134 A colorless liquid monomer represented by the following structural formula (Formula 61) was carried out in the same manner as in Example 132, except that 87.1 parts of diethylene glycol monomethacrylate of Example 132 was replaced with 80.1 parts of diethylene glycol monoacrylate. 153.6 parts were obtained.

[0146]

[Chemical formula 61] Example 135 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 134 was added to 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 134 except that 0.6 part was substituted,
152.9 parts of a colorless liquid monomer represented by the following structural formula (Formula 62) was obtained.

[0147]

[Chemical formula 62] Example 136 The procedure of Example 132 was repeated except that 87.1 parts of diethylene glycol monomethacrylate of Example 132 was replaced with 101.1 parts of dipropylene glycol monomethacrylate, and the liquid was a colorless liquid represented by the following structural formula (Formula 63). 173.5 parts of a monomer of

[0148]

[Chemical formula 63] Example 137 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 136 was added to 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 136 except that 0.6 part was substituted,
171.9 parts of a colorless liquid monomer represented by the following structural formula (Formula 64) was obtained.

[0149]

[Chemical 64] Example 138 A colorless liquid represented by the following structural formula (Formula 65) was performed in the same manner as in Example 132, except that 87.1 parts of diethylene glycol monomethacrylate of Example 132 was replaced with 94.1 parts of dipropylene glycol monoacrylate. 177.2 parts of the above monomer was obtained.

[0150]

[Chemical 65] Example 139 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 138 was replaced with 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 138 except that 0.6 part was substituted,
168.2 parts of a colorless liquid monomer represented by the following structural formula (Formula 66) was obtained.

[0151]

[Chemical formula 66] Example 140 87.1 parts of diethylene glycol monomethacrylate of Example 132 was added to polyethylene glycol monomethacrylate 143.0 represented by the following structural formula (A).
209.5 parts of a colorless liquid monomer represented by the following structural formula (B) (Chemical Formula 67) was obtained in the same manner as in Example 132 except that the parts were replaced.

[0152]

[Chemical formula 67] Example 141 100.6 parts of 3-isopropenyl-α, α-dimethylbenzylisocyanate of Example 140 was replaced with 4-isopropenyl-α, α-dimethylbenzylisocyanate 10
Similar to Example 140 except that 0.6 part was replaced,
205.9 parts of a colorless liquid monomer represented by the following structural formula (Formula 68) was obtained.

[0153]

[Chemical 68] Example 142 87.1 parts of diethylene glycol monomethacrylate of Example 132 was added to polyethylene glycol monomethacrylate 210.9 represented by the following structural formula (A).
The procedure of Example 132 was repeated except for replacing parts by parts to obtain 288.1 parts of a colorless liquid monomer represented by the following structural formula (B) (chemical formula 69).

[0154]

[Chemical 69] Example 143 100.6 parts of 3-isopropenyl-α, α-dimethylbenzylisocyanate of Example 142 is replaced with 4-isopropenyl-α, α-dimethylbenzylisocyanate 10
Similar to Example 142 except that 0.6 part was substituted,
285.9 parts of a colorless liquid monomer represented by the following structural formula (Formula 70) was obtained.

[0155]

[Chemical 70] Example 144 Example 144 is carried out in the same manner as Example 132, except that 87.1 parts of diethylene glycol monomethacrylate of Example 132 is replaced with 137.1 parts of polyethylene glycol monoacrylate represented by the following structural formula (A) (Chemical formula 71), Colorless liquid monomer 2 represented by the following structural formula (B)
08.6 parts were obtained.

[0156]

[Chemical 71] Example 145 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 144 was replaced with 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 144 except that 0.6 part was substituted,
210.6 parts of a colorless liquid monomer represented by the following structural formula (Formula 72) was obtained.

[0157]

[Chemical 72] Example 146 The procedure of Example 132 was repeated, except that 87.1 parts of diethylene glycol monomethacrylate of Example 132 was replaced with 204.5 parts of polyethylene glycol monoacrylate represented by the following structural formula (A) (Chemical Formula 73), Colorless liquid monomer 2 represented by the following structural formula (B)
82.9 parts were obtained.

[0158]

[Chemical formula 73] Example 147 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 146 was added to 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 146 except that 0.6 part was substituted,
285.2 parts of a colorless liquid monomer represented by the following structural formula (Formula 74) was obtained.

[0159]

[Chemical 74] Example 148 87.1 parts of diethylene glycol monomethacrylate of Example 132 was added to polypropylene glycol monomethacrylate 177. of the following structural formula (A).
The procedure of Example 132 was repeated, except that the amount was changed to 5 parts, to obtain 259.7 parts of a colorless liquid monomer represented by the following structural formula (B).

[0160]

[Chemical 75] Example 149 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 148 was replaced with 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 148 except that 0.6 part was substituted,
253.9 parts of a colorless liquid monomer represented by the following structural formula (Formula 76) was obtained.

[0161]

[Chemical 76] Example 150 87.1 parts of diethylene glycol monomethacrylate of Example 132 was added to polypropylene glycol monomethacrylate 263.m of the following structural formula (A).
The procedure of Example 132 was repeated, except that the amount of the monomer was changed to 7 parts to obtain 330.8 parts of a colorless liquid monomer represented by the following structural formula (B).

[0162]

[Chemical 77] Example 151 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 150 was replaced with 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 150 except that 0.6 part was substituted,
Thus, 327.6 parts of a colorless liquid monomer represented by the following structural formula (Formula 78) was obtained.

[0163]

[Chemical 78] Example 152 87.1 parts of diethylene glycol monomethacrylate of Example 132 was added to polypropylene glycol monoacrylate 172.8 represented by the following structural formula (A).
The procedure of Example 132 was repeated except for replacing parts by parts to obtain 239.4 parts of a colorless liquid monomer represented by the following structural formula (B) (Chemical Formula 79).

[0164]

[Chemical 79] Example 153 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 152 was replaced with 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 152 except that 0.6 part was substituted,
246.5 parts of a colorless liquid monomer represented by the following structural formula (Formula 80) was obtained.

[0165]

[Chemical 80] Example 154 Polypropylene glycol monoacrylate 258.5 represented by the following structural formula (A) (Chemical Formula 81) was obtained by converting 87.1 parts of diethylene glycol monomethacrylate of Example 132.
The procedure of Example 132 was repeated except for replacing parts by parts to obtain 333.2 parts of a colorless liquid monomer represented by the following structural formula (B) (Chemical Formula 81).

[0166]

[Chemical 81] Example 155 100.6 parts of 3-isopropenyl-α, α-dimethylbenzyl isocyanate of Example 154 was replaced with 4-isopropenyl-α, α-dimethylbenzyl isocyanate 10
Similar to Example 154, except substituting for 0.6 part,
327.9 parts of a colorless liquid monomer represented by the following structural formula (Formula 82) was obtained.

[0167]

[Chemical formula 82]

[0168]

Industrial Applicability The composite transparent molded article of the present invention obtained by laminating a high-hardness transparent resin on a transparent resin molded article has surface hardness, scratch resistance, rigidity, chemical resistance, heat resistance, weather resistance and resistance to abrasion. It has extremely excellent performance such as impact resistance. Therefore, the composite transparent molded body of the present invention is extremely useful as a raw material for a transparent material such as a glazing material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication C08F 12/34 MJY 7211-4J // B29K 33:04 69:00 (72) Inventor Kenichi Fujii Kanagawa 1190 Kasama-cho, Sakae-ku, Yokohama, Japan

Claims (10)

[Claims] 1. A pencil hardness of 4H or more and a Rockwell M on the surface of a transparent resin molding having a total visible light transmittance of 85% or more.
A composite transparent molded article having a flexural modulus of 350 kgf / mm ² or more, which is obtained by laminating a high-hardness transparent resin having a scale hardness of 100 or more and a total visible light transmittance of 85% or more to a film thickness of 0.2 mm or more. 2. The transparent resin molding is placed in a casting polymerization mold, and a monomer of a high hardness transparent resin is injected into the space and polymerization is performed. Composite transparent molding. 3. The composite transparent molded body according to claim 1, which is obtained by laminating a transparent resin molded body and a high-hardness transparent resin molded body. 4. The transparent resin molding is polymethylmethacrylate resin, polycarbonate resin, polystyrene resin, polyester resin, polyacetal resin, polysulfone resin, polyethersulfone resin, polyvinyl chloride resin, polyvinylidene chloride resin, epoxy resin. The composite transparent molded article according to any one of claims 1 to 3, which is a resin molded article selected from unsaturated polyester resin, polyurethane resin, diallyl phthalate resin, diethylene glycol bisallyl carbonate resin or acetyl cellulose resin. 5. A high-hardness transparent resin laminated on a transparent resin molding is at least represented by the following formula (1) (formula 1) or formula (2):
The composite transparent molding according to any one of claims 1 to 4, which is a resin having any of the structures represented by (Chemical Formula 1). [Chemical 1] 6. The composite transparent molded body according to claim 5, wherein the high-hardness transparent resin to be laminated on the transparent resin molded body is any of the resins described in (Resin-a) to (Resin-j) below. . Resin-a: a functional group represented by the following general formula (3) (chemical formula 2) in one molecule and a functional group represented by the following general formula (4) (chemical formula 2) or general formula (5) (chemical formula 2) A resin obtained by polymerizing a monomer (A) which also has a functional group Resin-b: a monomer (B) having m (m represents an integer of 1 to 6) at least one functional group selected from the group (A) and the following group of groups (Chemical Formula 3). A resin obtained by copolymerizing and -Resin-c: a resin obtained by copolymerizing a monomer (A) and a monomer (C) having two or more -SH groups in one molecule, -Resin-d: a monomer (A) A resin obtained by copolymerizing a monomer (B) and a monomer (C), and a resin-e: a monomer (B) and a monomer represented by the following general formula (6) A resin obtained by combining and copolymerizing a monomer (D) and (n + m) to be an integer of 3 or more, (In the formula, X represents an oxygen atom or a sulfur atom, R ₂ is a saturated aliphatic residue which may have a halogen atom, an oxygen atom, an alicyclic ring, a heterocycle or an aromatic ring in the residue, Alicyclic residue,
A heterocyclic residue, n is an integer of 1 to 4, when n = 1, X is an oxygen atom or a sulfur atom, and when n ≧ 2, X is all oxygen atoms or all sulfur atoms, or 1 ˜2 are oxygen atoms and the rest are sulfur atoms, or one is a sulfur atom and the rest are oxygen atoms) Resin-f: Monomer (B) and monomer (D) (n +
m) is a resin obtained by combining them so as to be an integer of 3 or more, and further copolymerizing with a monomer (C), Resin-g: In one molecule, the following general formula (7) A resin obtained by polymerizing a monomer (E) having a functional group represented by the following formula (5) (Chemical Formula 5) or a functional group represented by the following general formula (8) (Chemical Formula 5): Chemical 5] (In the formula, R ₁ represents a hydrogen atom or a methyl group) -Resin-h: a resin obtained by copolymerizing the monomer (B) and the monomer (E),-Resin-i: a monomer A resin obtained by copolymerizing (B) and a monomer (F) represented by the following general formula (9) (Chemical Formula 6) such that (n + m) is an integer of 3 or more, and ] (In the formula, R ₃ is -C (= O) -NH- group, -C (= S) -NH- group, -C (= O) -O
-Group or a saturated aliphatic residue which may have a functional group selected from -C (= O)-group (provided that each of the functional groups is bonded to an isopropenylphenoxy group on its left side). Group, an alicyclic residue and an aliphatic residue having at least one selected from the group consisting of an alicyclic group, a heterocycle, an aromatic ring and a hetero atom in the residue or a -C (= O)-group Where n is 1
Resin-j: a resin obtained by copolymerizing a monomer (B) with a monomer (G) represented by the following general formula (10) (Chemical formula 7): ] (In the formula, X is an oxygen atom or a sulfur atom, and R ₄ is an aliphatic residue, an alicyclic residue having or not having an oxygen atom, an alicyclic ring, a heterocycle, or an aromatic ring in the residue. Where l represents a number of 0 or 1, i and j are integers of 1 or more, and when l = 0, i
= J = 1 and l = 1, i + j is 4 or less, and j = 1
Is X is an oxygen atom or a sulfur atom, and when j ≧ 2, X is
Are all oxygen atoms or all sulfur atoms, or one is an oxygen atom and the rest is a sulfur atom, or one is a sulfur atom and the rest are oxygen atoms) 7. A transparent resin molded body is a polymethylmethacrylate resin molded body, a polycarbonate resin molded body, or a polycarbonate resin molded body having a polymethylmethacrylate resin or an acrylic photocurable resin as a mutual dissolution protection layer on the surface thereof. 7. The composite transparent molded body according to claim 6, wherein the high-hardness transparent resin laminated on the molded body is a resin of resin-a, b, or d. 8. The composite according to claim 5, wherein the high-hardness transparent resin to be laminated on the transparent resin molding is a resin having any of the following structural units (Structural Unit-1) to (Structural Unit-5). Transparent molded body. Structural unit-1: Structural unit represented by the following general formula (11) (Chemical formula 8) and / or (12) (Chemical formula 8), (In the formula, X represents an oxygen atom or a sulfur atom, and R ₁ represents a hydrogen atom or a methyl group.) Structural unit-2: the following general formula (13) (Chemical formula 9) and / or (14) (Chemical formula 9) A structural unit represented by: (In the formula, X is an oxygen atom or a sulfur atom, R ₂ is a saturated aliphatic residue which may have a halogen atom, an oxygen atom, an alicyclic ring, a heterocycle, or an aromatic ring in the residue, An alicyclic residue or a heterocyclic residue, R ₁ is a hydrogen atom or a methyl group, Y is any of the following groups (formula 10), n is an integer of 1 to 4, and m is 1 to Represents an integer of 6, (n + m) represents an integer of 3 or more, and when n = 1, X represents an oxygen atom or a sulfur atom,
When n ≧ 2, X is all oxygen atoms or all sulfur atoms, or one or two oxygen atoms and the rest are sulfur atoms,
Alternatively, one is a sulfur atom and the rest are oxygen atoms. -Structural unit-3: the following general formula (15) (chemical formula 11) and /
Or a structural unit represented by (16) (Chemical Formula 11), (In the formula, R ₁ represents a hydrogen atom or a methyl group) Structural unit-4: the following general formula (17) (Chemical formula 12) and / or
Alternatively, a structural unit represented by (18) (Chemical Formula 12): (In the formula, R ₃ is -C (= O) -NH- group, -C (= S) -NH- group, -C (= O) -O
-Group or a saturated aliphatic residue which may have a functional group selected from -C (= O)-group (provided that each of the functional groups is bonded to an isopropenylphenoxy group on its left side). Group, an alicyclic group residue, an aliphatic residue having at least one selected from the group consisting of an alicyclic group, a heterocycle, an aromatic ring or a hetero atom in the residue, or a -C (= O)-group Represents R ₁ , Y,
n and m represent the same meaning as described above.) Structural unit-5: Structural unit represented by the following general formula (19), (20) (Chemical formula 13) and / or (21), (22) (Chemical formula 14) [Chemical 13] [Chemical 14] (In the formula, X is an oxygen atom or a sulfur atom, and R ₄ is an aliphatic residue, an alicyclic residue having or not having an oxygen atom, an alicyclic ring, a heterocycle, or an aromatic ring in the residue. R ₁ represents a hydrogen atom or a methyl group, l represents a number of 0 or 1, i and j are integers of 1 or more, and when l = 0, i = j = 1, and when l = 1, i + j. Is 4 or less, when j = 1, X is an oxygen atom or a sulfur atom, and when j ≧ 2, X is all oxygen atoms or all sulfur atoms, or one is an oxygen atom and the rest is a sulfur atom, or (One is a sulfur atom and the rest are oxygen atoms.) 9. A glazing material using the composite transparent molded body according to claim 1. 10. A polymerizable monomer represented by the general formula (23) (formula 15). [Chemical 15] (In the formula, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or a methyl group, k represents an integer of 2 to 10, and the position of the substituent on the aromatic ring represents p-position or m-position).