JPS62212437A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition which is given high mold releasability and properties necessary for the material of an optical disk base and is freed of bleeding of a releasing agent, by mixing a specified acetal compound with a specified mercapto compound, a specified reactive unsaturated compound and a fourth component for improving mold releasability. CONSTITUTION:This curable composition contains the following four components (a)-(d). (a): a compound having at least two unsaturated cycloacetal groups per molecule, (b) a compound having at least two mercapto groups per molecule, (c) a compound having at least two reactive unsaturated bonds per molecule, and (d) a silicone compound (d-1) having at least one mercapto group and/or an ester compound (d-2) of a carboxylic acid having at least one mercapto group per molecule with a 4C or higher linear or branched alcohol.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a curable composition that can be suitably used as an optical material such as an optical information recording disk and a plastic lens.
In particular, the present invention relates to a curable composition that can be suitably used as a substrate material for optical discs such as video discs, audio discs, and optical memory discs that record and reproduce information such as images and audio using light.

(Prior Art) Various materials have been studied for substrate materials for optical disks.

Acrylic resin has excellent transparency, but has a high water absorption rate and warps due to moisture absorption.

It also has the disadvantage of causing large dimensional changes due to moisture absorption.

Although polycarbonate resin does not have the disadvantages of acrylic resin, it has poor moldability and is prone to birefringence, which causes noise, due to molecular orientation during molding.To counter this, it is necessary to lower the molecular weight to improve moldability. In this case, mechanical properties such as surface hardness deteriorate, making it impossible to satisfy both birefringence and mechanical properties.

Furthermore, in order to increase the read speed from optical discs, it is necessary to use a laser with high output, but since neither the above-mentioned acrylic resin nor polycarbonate resin has high heat resistance, optical discs made of these materials cannot be used for printing. There is a dissatisfaction with the inability to support higher readout speeds due to the risk of groups and pits melting and disappearing.

On the other hand, forming the substrate from glass has also been proposed, but there are problems such as increased weight and poor productivity.

In recent years, thermosetting (photo)curable resins have been attracting attention as materials that can address the problems of substrate materials as described above. Thermal (photo)curable resins are seen as promising new optical disk substrate materials because their physical properties such as birefringence, water absorption, and heat resistance can be controlled relatively easily, and productivity has been improved through reaction injection molding.

However, this thermosetting (photo)curable resin has the disadvantage that the molded substrate cannot be easily released from the mold during molding. For this reason, distortion may occur in the molded substrate during demolding, or
There were problems such as damage to the surface of the stamper of the mold.

One way to deal with this problem is to apply a mold release agent to the surface of the mold, but such a coated mold release agent adheres to the surface of the molded product, which is undesirable as it causes reading errors and the like. On the other hand, it has been proposed to add a mold release agent to thermosetting (photo)curable resins, but conventionally proposed internal mold release agents tend to bleed due to temperature rise when irradiated with laser light. This has the disadvantage that it tends to ooze out onto the surface of the molded product, reducing the reliability of the optical disc.

(Means for Solving the Problem) As a result of intensive research in order to solve the above-mentioned problems, the present inventors have discovered that the following curable composition has various physical properties required for materials such as optical disk substrates. The present inventors have discovered that they have both high mold releasability and no bleeding of the mold release agent, and have come up with the present invention.

First, the curable composition of the first invention comprises a compound having at least two unsaturated cycloacetal groups per molecule (hereinafter referred to as an acetal compound (A)).
(hereinafter abbreviated as mercapto compound (B)) and a compound having at least two mercapto groups per molecule (hereinafter abbreviated as mercapto compound (B))
(1) A compound having at least two reactive unsaturated bonds per molecule (hereinafter abbreviated as a reactive unsaturated bond compound (C)); and (1) a silicone compound having at least one mercapto group in one molecule. and/or curing consisting of an ester compound (hereinafter abbreviated as compound (D)) obtained by reacting a carboxylic acid having at least one mercapto group in one molecule with a linear or branched alcohol having 4 or more carbon atoms. It is a sexual composition.

Further, the curable composition of the second invention contains at least compound (A), compound (B), and compound (C) among the compounds blended in the composition of the first invention; Consisting of a compound having a total of two methacryloyl groups and/or acryloyl groups, and an alkyl group having 8 or more carbon atoms and/or its halogen atom substituted product (hereinafter abbreviated as alkyl compound (E)) It is a curable composition.

Hereinafter, the curable composition of the present invention will be explained in detail.

±Utachi5± First, each of the ingredients forming the curable compositions of the first and second inventions will be explained.

(A) Acetal compound The acetal compound (A) used in the curable composition of the present invention refers to an unsaturated cycloacetal group represented by (unsaturated dioxane type) and/or (unsaturated dioxolane type). It is an unsaturated cycloacetal compound having at least two acetals in one molecule.

Examples of the acetal compound (A) suitably used in the curable composition of the present invention include the following compounds (I) to (V).

(i+diarylidenepentaerythritol, triarylidene sorbitol, diarylidene-2, 2, 6, 6
-titramethylolcyclohexanone or mixtures thereof.

(fi) (a) Diarylidenepentaerythritol and/or Diallylidene-2, 2, 6, 6-titramethylolcyclotoJE-None and (b) Ethylene glycol, diethyl glycol, triethylene glycol, propylene Glycol, dipropylene glycol, 1,3-butanediol, 1,6-
Hexanediol, polyethylene glycol, hydrogenated bisphenol A, bisphenol-ethylene oxide adduct, bisphenol A-propylene oxide adduct, trimethylolpropane, trimethylolethane,
Pentaerythritol, dipentaerythritol.

Polyols such as ethylene oxide adducts of phthalic acid, isophthalic acid and terephthalic acid, and polyesters containing terminal hydroxyl groups with 9 molecules f11,500 or less.

(C) dithioglycol, dibentenedimel butane,
Water per molecule, such as polythiols such as ethylcyclohexyl dimercaptan and 1,6-hexane dimercaptan, thioglycolic acid, β-mercaptopropionic acid, or ester compounds obtained by reacting mercaptosuccinic acid with the above polyols. M group and (
or) a compound containing two or more mercapto groups in total, (d
) Phenol, cresol, and phenols such as novolak, bisphenol F, and bisphenol A obtained by formalin condensation of these.

(e) Arylsulfonamides such as benzenesulfonamide, 0-toluenesulfonamide, P.-toluenesulfonamide, chlorobenzenesulfonamide, or (f) a reaction product with a mixture thereof.

(To) Monoallylidene trimethylolpropane and/or monoallylidene trimethylolethane and isocyanates such as tolylene diisocyanate, polyalkylene allyl isocyanate, metaphenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophonyl diisocyanate, etc. Reaction products with compounds.

(f) monoallylidene trimethylolpropane and/or monoallylidene trimethyloleethane and succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, te) rhydolphthalic anhydride, Addition half-esterified product with hexahydrophthal S anhydride.

(V) Addition half-esterified product of monoallylidene trimethylolpropane and/or monoallylidene trimethyloleethane with carboxylic acid anhydride, polyglycidyl ether type epoxy compound, phthalic acid, adipic acid, dimer acid, etc. A compound obtained by reacting with an epoxy compound such as a glycidyl ester type epoxy compound.

(B) Mercapto Compound The mercapto compound (B) used as the second component of the curable composition of the present invention refers to at least 2 mercapto compounds per molecule.
It is an aliphatic or aromatic polymercaptan having 2 mercapto groups.

Examples of the mercapto compound (B) suitably used in the composition of the present invention include the compounds shown in the following (I) to (V).

(+) Dibentenedimerbutane, ethylcyclohexyldimercaptan, 1,6-hexane dimercaptan.

(i) An ester compound of a mercapto compound having a carboxyl group and a polyhydric alcohol. Examples of the mercapto compound having a carboxyl group include thioglycolic acid, β-mercaptopropionic acid, and mercaptosuccinic acid. Further, examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, trimethylolpropane, and trimethylolethane.

(to) 1 water at the carbon atom in the β-position relative to the mercapto group
A compound with one group.

A compound obtained by the reaction of axial epoxy resin with hydrogen sulfide.

(V) A compound obtained by reacting an epoxy resin with thioglycolic acid.

(C) Reactive unsaturated bond compound The reactive unsaturated bond compound (C) which is the third component of the curable composition of the present invention is a compound having at least two reactive unsaturated bonds per molecule. Various compounds can be used as long as they can be copolymerized with the acetal compound (A) and mercapto compound (B) and can be uniformly mixed.

Such compounds include bisphenols (C-1
), isocyanuric acid derivative (C-2).

Triazine compounds (C-3), other compounds (C-
4). Among these, bisphenols (
C-1), isocyanuric acid derivative (C-2), triazine compound (C-3), etc., the curable composition containing these is heat resistant.

It is preferable because it has particularly excellent water resistance.

These compounds will be explained below.

The bisphenols (C-1) suitable for use as the reactive unsaturated bond compound which is the third component of the composition of the present invention are those having a total of at least two acryloyl groups and/or methacryloyl groups per molecule. It is a bisphenol having a group.

Bisphenols (
C-1) is exemplified by the following formula (1).

(R++7g X→R2)n2−−−−− (1)(1
) In the formula, n I +n2 is an integer of 1 to 3.

In formula (1), X has a structure represented by formulas (2) to (7).

(Sawa Y÷ -------(2) Here, Y in formula (2) has the structure shown in formulas (8) to (16), etc.

-C-CH2-CH----(8) SaR3 H3 -CH2----(9) -C----(
10) H3 Furthermore, R1 and R2 in formula (1) include those having the structure shown in formula (17).

Here, in formula (17), R3 and R4 are hydrogen (H).

Methyl W (Me), ethyl group (Et) and its halogen atom isoanalytes. Further, m is an integer from 0 to 6.

Each of the above compounds can be used alone or as a mixture of two or more.

Isocyanuric acid derivative (C-2) suitable for use as the reactive unsaturated bond compound which is the third component of the composition of the present invention
is an isocyanuric acid derivative having a total of at least two acryloyl groups and/or methacryloyl groups per molecule.

Examples of the isocyanuric acid derivative (C-2) include the following compounds.

a) A reaction product obtained by reacting acrylic acid and/or methacrylic acid with a reaction product obtained by adding ethylene oxide, propylene oxide, etc. to isocyanuric acid.

b) A product obtained by adding epichlorohydrin to isocyanuric acid and adding 12-hydrochloric acid to it and ethylene glycol,
A reaction product obtained by reacting a reaction product with a polyhydric alcohol such as propylene glycol or glycerin with acrylic acid and/or methacrylic acid.

C) A reaction product obtained by reacting a reaction product of isocyanuric acid, ethylene chlorohydrin, and allyl chloride with acrylic acid and/or methacrylic acid.

d) Reaction products of adducts of isocyanuric acid and ethylene oxide with glycidyl acrylate and/or glycidyl methacrylate.

e) A reaction product of a reaction product of isocyanuric acid and chloroacetamide that is methylolated with formalin or the like, and acrylic acid and/or methacrylic acid.

f) A methylolated reaction product of isocyanuric acid and acrylamide, and a reaction product of acrylic acid and/or methacrylic acid.

a) A compound in which a part of the acrylic group or methacrylic group of the reaction product of a) to f) is substituted with a saturated acyl group.

These compounds can be used alone or in combination of two or more. This isocyanur! ! Representative derivatives (C-2) include tris(2-acryloylxyethyl)isocyanurate, tris(2-
methacryloylxyethyl) isocyanurate, di(2
-acryloylxyethyl)-2hydroxyethyl isocyanurate, di(2methacryloylxyethyl)2hydroxyethyl isocyanurate, di(2-acryloylxyethyl)2acetoxyethyl isocyanurate,
Di(2-methacryloylxyethyl)acetoxyethyl isocyanurate, di(2-acryloylxyethyl)-
Allyl isocyanurate.

Examples include di(2methacryloylxyethyl)-allylin cyanurate.

Note that the total number of acryloyl groups and/or methacryloyl groups in this molecule may be 21 m or more.

I G-8 1 The triazine compound (C-3) suitable for use as the reactive unsaturated bond compound which is the third component of the composition of the present invention is a triazine compound (C-3) having at least one triazine ring per molecule. And 1
A compound having a total of at least two acryloyl groups and/or methacryloyl groups per molecule, and the following (18
) or compounds obtained by oligomerizing these with formalin, polyhydric alcohol, ethylene oxide, etc.

(18) In the formula, X, Y, and Z are hydrogen, an alkyl group, or an alkoxyl group modified with (meth)acrylic. However, R and R are hydrogen, or an aliphatic group such as a methyl group, an ethyl group, or a propyl group. Alkyl group, aromatic alkyl group such as benzyl group, or ÷CH2-CH2-0÷C0-C■
CH2x (n-0 to 4.X-hydrogen or alkyl group).

Typical examples of this triazine compound (C-3) include (1) N, N'-bis(meth)acryloylmethyl-N, N', N", N"-tetraki, sumethoxymethylmelamine; N, N, N', N''-tetrakis(meth)acryloylmethyl-141, f411-bisethoxymethylmelamine, (2) N, N, N', N', N'', N''-hexakis (2- (meth)acryloylethoxymethyl)melamine, (3) 2,4-bis[[N,N-bis[(
2-(meth)acryloylethoxy)ethoxymethyl]
]-amino]-〇-ethoxy-1,3,5-triazine,
(4) 2.4-bis[p-(2-(meth)acryloylethoxy)phenyloxy]-6-[(N,H-bis[(2-(meth)acryloylethoxy)ethoxymethyl J]amino] - 1,3,5-triazine, (5)
2.2-bis[4-[[N,N',N'-trismethoxymethyl-N',N''-(2-(meth)acrylic0
ylethoxy)methyl]melaminyloxy]phenyl J
Examples include propane.

In addition, as polyhydric alcohols used for oligomerization,
Examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,6-hexanediol, hydrogenated bisphenol A, trimethylolpropane, pentaerythritol, ethylene oxide adducts of phthalic acid, isophthalic acid, and terephthalic acid. It will be done.

In addition, triazine ring 11 in the molecule! The number of acryloyl groups and/or methacryloyl groups in each molecule is not limited at all as long as it is 2 or more in total, but considering the balance between the water absorption effect due to ester bonds and the improvement in heat resistance due to increased crosslink density, the number of triazine groups in one molecule is The number of functional groups per 1131 is within the range of 4 to 6'! It's like f1.

Part 1-81 Examples of other compounds (C-4) suitable for use as the reactive unsaturated bond compound which is the third component of the composition of the present invention include the following.

■Ethylene glycol di(meth)acrylate.

Diethylene glycol di(meth)acrylate.

Triethylene glycol di(meth)acrylate.

Polyethylene glycol di(meth)acrylate.

Brobylene glycol di(meth)acrylate.

Voribropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate.

Trimethylolpropane] Su(meth)acrylate,
Methacryloyl compounds such as pentaerythritol tri(meth)acrylate, diglycidyl bisphenol A di(meth)acrylate, pentaerythritol tetramethacrylate, bisphenol A epoxy dimethacrylate, ■vinyl compounds such as divinylbenzene and divinyl adipate, ■ethylene glycol diacrylate, Acryloyl compounds such as trimethylolpropane triacrylate, pentaerythritol tetramethacrylate, bisphenol A epoxy acrylate, ■ diallyl phthalate, diallyl succinate.

Diallyl adipate, triallyl isocyanurate, diglycol bisallyl carbonate, diallyl maleate, diallyl fumarate.

(D) Compound (D) Next, the compound (D) blended as the fourth component in the curable composition of the first invention will be explained.

Compound (D) is a silicone compound (D-1) having at least one mercapto group in one molecule and/or a carboxylic acid having at least one mercapto group in one molecule and a linear chain having 4 or more carbon atoms. Or it is an ester compound (D-2) with a branched alcohol. Compound (D), which is the fourth component, functions to improve the mold release properties of the resulting curable composition.

Examples of the silicone compound (D-1) having at least one mercapto group in one molecule include the following compounds. That is, they are compounds as shown in formulas (19) and (20).

[Viscosity 1,0-100Cp at 25°C] [J=0-a
;k,j=o~3;k+j-3R1,R2
is an alkyl group such as methyl, ethyl, etc.) Typical compounds include mercapto-modified silicone oil as shown in formula (1), and H5A-ASi→OMe)3.

Further, as the ester compound (D-2) of a carboxylic acid having at least one mercapto group in one molecule and a linear or branched alcohol having 4 or more carbon atoms, the following compounds are exemplified.

That is, it is a compound as shown in formula (21).

Here, when the number of carbon atoms is 3 or less, desired mold release properties cannot be obtained.

HS+CH,+HC-0-R---(21) [R is CS
~C18 straight chain or branched alkyl group, n=1-5
] Among them, a representative compound is thioglycolic acid 2-
Ethylhexyl, pentyl thioglycolate, 2-ethylhexyl γ-mercaptobutyrate, γ-mercaptobutyric acid-
Examples include isoacyl.

The most important part in the first invention is to polymerize and add the fourth component, the compound (D), to the reactive unsaturated bond compound (C) in advance. Thereby, it is possible to prevent the bleeding phenomenon of the female component (compound (D)) after the composition is cured, and it is also possible to mold a transparent resin with extremely good mold releasability.

Generally, when a heat-resistant monomer with a heat-resistant skeleton such as bisphenol, triazine, or isocyanuric acid is blended,
Since mold release often deteriorates, it is necessary to use a mold release agent, but if an acrylic-modified mold release agent is simply blended, a bleed phenomenon will occur after molding.

On the other hand, as mentioned above, the mold release agent component (compound (D)
) is bonded to the monomer before polymerization, it is possible to achieve excellent mold releasability without the bleed phenomenon after molding. This is thought to be effective for plastic lens molding using acrylic thermosetting resins, and is expected to greatly open the door to RIM molding using these resins.

The polymerization of compound (D), which is a mold-releasing component, and reactive unsaturated bond compound (C) is carried out at a temperature of 45°C to 55°C.
Complete by performing from 0 minutes to 1 hour - at this time, 11
If the temperature is increased too much, polymerization will proceed too much and fluidity will be lost.
If the temperature is too low, polymerization will be insufficient, resulting in the disadvantage that the cured product will be extremely yellow in color due to the influence of residual mercapto groups.

(E) Alkyl Compound (E) Next, the compound (E) to be blended as the fourth component in the curable composition of the second invention will be explained.

The alkyl compound (E) is at least 2 per molecule.
It is a compound having an acryloyl group or a methacryloyl group, an alkyl group having 8 or more carbon atoms, and/or a halogen-substituted product thereof. This fourth component, the alkyl compound (E), also serves to improve the mold releasability of the resulting curable composition.

As such an alkyl compound (E), the following (1
A typical example is one obtained by reacting the compounds shown in ) and (ii).

(1) Trivalent or higher alcohols such as glycerin, trimethylolpropane, and pentaerythol and acrylic acid,
Methacrylic acid and/or its acid chloride.

(1) Octylic acid, nonanoic acid, decanoic acid, hexadecanoic acid, stearic acid and/or acid chloride thereof.

In addition, an amino group and an N-methyl group.

Acryloyl group with active halogen group as the reaction point.

Compounds into which a methacryloyl group or an alkyl group has been introduced can also be used.

(F) Other additives The curable composition of the present invention includes not only various initiators and sensitizers, but also antioxidants, stabilizers, mold release agents, dyes, antistatic agents, antifogging agents, and interfaces. Additives such as an activator, a leveling agent, a polymerization regulator, and an ultraviolet absorber can be added as necessary.

In addition, as long as it is copolymerizable with the acetal compound (A), mercapto compound (B), and reactive unsaturated bond compound (C) within a range that does not significantly impair the essence of the composition, and is uniformly mixed with the compound, It is also possible to add reactive monomers or oligomers.

The blending ratio of each of the above components is not particularly limited, but is preferably blended within the following range.

In the case of this composition, the blending ratio of the acetal compound (A) and the mercapto compound (B) is 1:1 to 1:1 in terms of the ratio.
It is desirable that it be about 0.5.

When the amount of the acetal compound (A) is large, curing takes a long time and the molded product is likely to have unevenness. Furthermore, if the amount of the mercapto compound (B) is extremely large, the resulting molded product may have an unpleasant odor or have a decrease in physical properties such as hardness.

In addition, in order to obtain a curable resin, the total number of unsaturated cycloahital groups per molecule of the acetal compound (A) and the number of mercapto groups per molecule of the mercapto compound (B-) must be It is necessary that the number is 4 or more, preferably 5 or more.

The blending ratio of the third component, the reactive unsaturated bond compound (C), is not particularly limited, but if the amount used is too large, the hardness will be too high and the resulting cured product will become brittle. Moreover, if the amount used is too small, the desired heat resistance cannot be obtained. For this reason, the blending ratio of the reactive unsaturated bond compound (C) is 0 to 1 equivalent of the acetal compound (A).
．． It is desirable that the amount is 2 to 3 equivalents, more preferably 0.5 to 5.4 equivalents.

Next, the blending ratio of the fourth component added to improve the mold releasability of the curable composition will be explained. This Ii4
If the amount of the component blended is small, sufficient mold releasability will not be achieved, and if it is too large, problems such as a decrease in hardness and heat resistance will occur. For these reasons, the blending ratio of compound (D) in the curable composition of the first invention is preferably 3 to 5 phr, more preferably 1 to 10 phr.

Further, the blending ratio of the alkyl compound (E) in the curable composition of the second invention is such that the above compound (A> (B)
(C)+7) Combined 1ff11 hit 1! IG, JJL 0.
01 to 10 equivalents is more preferably 0.1 to 5 equivalents.

As a method for curing the composition of the present invention, first, each of the above-mentioned compounds (A), (B), (C) and (D) or (E
) are mixed uniformly at the specified ratio.

This mixture is then injected into a mold of a predetermined shape made of, for example, glass, ceramic, plastic, rubber, etc., and cured by the method described below.

(1) Method of irradiating active energy rays This method is
This is a method of curing a composition by irradiating it with active energy rays such as gamma rays, X-rays, ultraviolet rays, and electron beams.

The amount of irradiation energy should generally be 0.01 J/cj or more and 500 J/d or less, particularly 0.1 J/cj or more and 500 J/d or less.
It is preferably within the range of ~100 J/d. If the irradiation energy amount is less than 0.01 J/-, the crosslinking reaction will be incomplete and curing will be insufficient. On the other hand, if irradiation exceeds 500 J/-, a part of the resulting cured product (resin) will deteriorate or become colored, making it impossible to obtain a good information recording disc.

The irradiation may be divided into two or more times or may be performed at once. If necessary, additives such as photosensitizers and stabilizers described in JP-A-58-175877 may be added. This method is described in Japanese Patent Application Laid-Open No. 59-860.
01 and Japanese Patent Application Laid-Open No. 59-89330.

(2) Method using heat When curing the mixture using heat, the heating temperature is:
Although it varies depending on whether or not a polymerization initiator is used, their type and blending ratio, the temperature is usually room temperature to 300°C, and particularly preferably 50 to 130°C. If the heating temperature is lower than room temperature, the curing time will be longer, resulting in poor productivity. On the other hand, if the temperature exceeds 300°C, there will be a problem of deterioration due to heat.

In addition, the heating time depends on the temperature and whether or not a polymerization initiator is used.
Although it varies depending on the type and usage ratio, it is generally 0.1 to 100 hours, and particularly preferably 1 to 20 hours.

By using a polymerization initiator, curing time can be shortened. In this case, if the amount of polymerization initiator used is too large, the resulting cured product may be colored or become brittle, which is not preferable. Therefore, in consideration of the balance between the physical properties and productivity of the cured product obtained, the amount of the polymerization initiator used is 100% of the above mixture.
The opening is 10 times or less, usually 51m or less, relative to the overlapped portion.

Examples of the polymerization initiator suitably used here include those described in JP-A-55-105201.

(3) A method of irradiating active energy rays higher than other methods and a method using heat can also be used in combination.

Furthermore, when producing a resin by curing this kind of polymerizable monomer or a mixture thereof, it can also be cured by irradiating it with ultrasonic waves, laser, etc., which are widely practiced.

In addition, if necessary, the obtained cured product may be heated at 30 to 200°C.
Annealing may preferably be performed at 60 to 130°C.

(Function) The curable composition of the present invention exhibits excellent physical properties that cannot be achieved with the individual components alone, since each component complements each other's physical properties.

That is, in the curable composition of the present invention, the hardness and heat resistance of the cured product obtained from the acetal compound (A) and the mercapto compound (B) are supplemented by the reactive unsaturated bond compound (C), It is a practical material with well-balanced physical properties such as flexibility, water resistance, heat resistance, and hardness.

By blending the compound (D) or the alkyl compound (E) as a mold release component with this, the curable composition of the present invention has a low surface energy, and therefore a cured product with excellent mold release properties. can be molded, and the bleed phenomenon does not occur.

(Example) Hereinafter, the curable composition of the present invention will be described in more detail with reference to Examples.

First, a compound (
Various curable compositions of the first invention containing D) were prepared, and the physical properties of the molded bodies thereof were investigated.

Example 1 Diarylidene-2,2,6,6-tetramethylolcyclohexanone 25.09 was mixed with i, 1. i-trimethylolpropane tri(β-mercapto)propionate 2
5. It was dissolved in a mixed solution of OQ and 1,1.1-trimethylolpropane triacrylate 30Q, and 0.49 g of benzophenone was added to obtain a composition.

Separately, mercapto-modified silicone oil (X-22-980 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 2,2-bis[4-(2-acryloylethyloxy)phenyl]propane 60Q.
2. After adding Oq, the mixture was vigorously stirred at 50°C for 15 minutes. Thereafter, this product was added to the previously prepared composition and thoroughly mixed and stirred. This composition was poured into a mold made of glass with a finished surface, a gasket, etc., and was heated approximately 100 times from a distance of 15α on both sides using a 3kW metal halide lamp.
Polymerized by UV irradiation for seconds, diameter 120aw + q thickness 1.2
A uniform, colorless and transparent molded product of footwear was obtained.

Example 2 Diarylidenepentaerythritol 309, glycerin tetrathioglycolate 3G9, ethylene glycol diacrylate 60Q, and azobisisobuty[1 nitrile (AIBN) 0.200] were added and thoroughly stirred to dissolve the composition. Separately, 3.50 2-ethylhexyl thioglycolate was added to tri(2-acryloylethyloxy)isocyanutate 80Q, stirred vigorously at 45°C for 20 minutes, added to the previously prepared composition, and thoroughly mixed and stirred. did. This composition was poured into a predetermined mold, and
After holding at ℃ for 30 minutes, increase to 90℃ at a rate of 10℃ per hour.
The temperature was raised to 90°C, and the opening was held for 3 hours, followed by curing treatment at 120°C for 2 hours.

Example 3 Diarylidene erythritol 279 and 1,6-hexane dimercaptan 20Q were dissolved in pentaerythritol tetraacrylate 40Q, and benzoin isopropyl ether o and os g were added to obtain a composition. Separately, N,N',N',N",N"-hexakis(2-acryloylethoxymethyl)melamine 30Q
Silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. (Ni814-80)
2) 2. OQ was added and reacted at 50°C for 20 minutes, then added to the regulator composition and thoroughly mixed and stirred. This was cured and molded in exactly the same manner as in Example 1.

Comparative Example 1 The only difference from Example 1 was that no silicone oil was added.

Comparative Example 2 The only difference from Example 1 was that silicone oil was added after all the components other than silicone oil were mixed and dissolved.

In this case, 2.2-bis[4-(
2-Acryloylethyloxy)phenyl]propane and silicone oil do not react.

Comparative Example 3 The only difference from Example 3 was that no silane coupling agent was added.

Comparative Example 4 The only difference from Example 3 was that the silane coupling agent was added after all the components other than the silane coupling agent were mixed and dissolved.

For this item, N, N, N', N
',N'',N''-hexakis(2-acryloylethoxymethyl)melamine and the silane coupling agent do not react.

Comparative Example 5 The only difference from Example 2 was that the same amount of methyl thioglycolate was used instead of 2-edylhexyl thioglycolate.

Comparative Example 6 The only difference from Example 2 was that thioglycol M2-ethylhexyl and tri(2-acryloylethyloxy)isocyanutate were not added.

Comparative Example 7 Polycarbonate (Panlite optical grade manufactured by Yojin Kasei Co., Ltd.) was injection molded.

Comparative Example 8 Polymethacrylic acid medyl (Barabella 1-F1000a manufactured by Kyowa Gas Chemical Industry Co., Ltd.) was injection molded.

The following physical properties of the obtained molded body were investigated.

(1) Heat resistance (HOT) Tested according to ASTM D-648 method.

The load was 66 psi.

(2) Water absorption The molded body was measured at 23% by the method of ASTM D-570.
It was tested by immersing it in water at ℃ for 24 hours.

(3) Birefringence Using an automatic ellipsometer, the birefringence at each point was measured while rotating the disk molded body. The light source is 1e-N+
The wavelength of 3 lasers is 632.8 nm. Measured values indicate double bath values. Birefringence is the average of the absolute values of retardation and is expressed in nm.

(4) Transparency It shows the light transmittance at a wavelength of 780 na+.

(5) Mold releasability: 120, the number of sheets that could be released from the mold without cracking at all during the demolding operation out of 100 φ1.2Mt flat samples molded.

(6) Bleed of mold release agent Aluminum was sputtered on the flat plate after molding for about 2000 tons, and the surface was observed and judged.

The results are shown in Table 1.

Table 1 Next, a curable composition of the second invention in which an alkyl compound (E) is added to an acetal compound (A), a mercapto compound (B), and a reactive unsaturated bond compound (C). An example will be described below.

Example 4 212 g of diarylidene pentaerythritol was dissolved in 216 g of pentaerythritte tetrathioglycolate,
Heated at 50°C for 30 minutes with stirring.

Next, tris(2acryloylxyethyl)isocyanurate (22) formula 250Q, trimethylolpropane triacrylate 430 g, compound 11Q represented by formula (23), and benzoin isopropyl ether 0.4 g were added to this mixed solution. In addition, the mixture was stirred at 45° C. until it became uniform, to obtain a transparent curable composition.

This composition was poured into a glass mold equipped with a stamper and assembled using a gasket, and irradiated with ultraviolet rays for 30 seconds using a 3 kW metal halide lamp from a distance of 15 cm from the mold to obtain a colorless and transparent molded product.

Example 5 294 g of diarylidene-2,2,6,6-tetramethylolcyclohexanone and 205 g of 1,1.1-trimethylolpropane trithioglycolate were added, and 5
The mixture was heated at 0°C for 30 minutes with stirring to obtain a uniform U mixture. Next, bisphenol A diacrylate 1009, pentaerythritol tetraacrylate 100Q, and benzophenone o and sg were added and mixed with the above mixture to obtain a uniform mixture.

Next, 300 g of the reaction product of the compound of formula (24) and off-thyroyl chloride was added and thoroughly stirred to obtain a curable composition.

This product was molded using the same apparatus as in Example 4 to obtain a transparent molded product.

υ Example 6 1.1.1 for 212 g of diarylidene pentaerythritol
-Trimethylolpropane trithioglycolate 205
g was added thereto and heated at 50° C. for 30 minutes with stirring to obtain a homogeneous mixed solution. Trimethylolpropane triacrylate 400 to l and axis +NJ'+N' +H” +
H“-Hexakis (2-acryloylethoxymethyl)
Melamine 200Q and azobisisobutyronitrile 0.8
g and stirred, and further mixed with the compound represented by the above formula (23) to obtain a homogeneous liquid mixture. These liquid mixtures were mixed to obtain a transparent curable composition.

This material was poured into a glass mold and heated at 90° C. for 8 hours, and then the mold was released to obtain a transparent molded product.

Example 7 The only difference from Example 4 was that the compound represented by formula (22) was not added.

Comparative Example 9 This differs from Example 4 only in that the compound represented by formula (23) is not added.

Comparative Example 10 This differs from Example 5 only in that the compound represented by formula (24) is not added.

Comparative Example 11 This differs from Example 4 only in that a compound represented by formula (25) is added instead of the compound represented by formula (23).

CH3-fcH,40-(,-CHtomiCH2--(2
5) Comparative Example 12 Polymethyl methacrylate tree! (parapet rio.

Comparative Example 13 Injection molded product of polycarbonate resin (Panlite optical grade: manufactured by Yojin Kasei Co., Ltd.) Disk-shaped moldings obtained in Examples 4 to 7 and Comparative Examples 9 to 13 The body was examined for heat distortion temperature (80 cm), water absorption, zero birefringence, surface hardness, Izot impact value, brightness, and m-type property.

surface hardness By Percoll hard method.

Tested according to ASTM D-256 with Izot II shock value (■) notch.

Other measurement methods are the same as those described above.

The results are shown in Table 2.

Table 2 In the above description, the curable composition of the present invention is used for discs that perform recording and reproduction using light, particularly disc substrates thereof, but the present invention is not limited thereto. without plastic lenses or other information recording discs,
For example, it can be used for capacitance conversion type information recording discs.

(Effects of the invention) The curable composition of the invention has heat resistance, water resistance, impact resistance,
It becomes a molding material that has physical properties such as optical homogeneity, transparency, and surface hardness in a well-balanced manner, has further excellent mold release properties, and is free from the bleed phenomenon after molding. Therefore,
The curable composition of the present invention can efficiently produce optically reliable optical disk substrates, high-quality plastic lenses, etc., and is suitable as an optical material.

Claims (1)

[Scope of Claims] (1) [a] A compound having at least two unsaturated cycloacetal groups per molecule; [b] A compound having at least two mercapto groups per molecule; [c] 1 A compound having at least two reactive unsaturated bonds per molecule; [d] A silicone compound having at least one mercapto group in one molecule and/or a carboxylic acid having at least one mercapto group in one molecule. A curable composition comprising an ester compound obtained by reacting the compound with a linear or branched alcohol having 4 or more carbon atoms. (2) A patent characterized in that the compound [c] having at least two reactive unsaturated bonds per molecule is a bisphenol having a total of at least two acryloyl groups and/or methacryloyl groups per molecule A curable composition according to claim 1. (3) The compound [c] having at least two reactive unsaturated bonds per molecule is an isocyanuric acid derivative having a total of at least two acryloyl groups and/or methacryloyl groups per molecule. A curable composition according to claim 1. (4) The compound [c] having at least two reactive unsaturated bonds per molecule has a total of at least two acryloyl groups and/or methacryloyl groups per molecule, and at least one triazine ring. The curable composition according to claim 1, which is a compound having the following properties. (5) [a] A compound having at least two unsaturated cycloacetal groups per molecule; [b] A compound having at least two mercapto groups per molecule; [c] At least two mercapto groups per molecule. a compound having a reactive unsaturated bond; [e] having a total of at least two acryloyl groups and/or methacryloyl groups per molecule, and having a carbon number of 8;
A curable composition comprising a compound having the above alkyl group and/or its halogen atom substituted product. (6) A patent characterized in that the compound [c] having at least two reactive unsaturated bonds per molecule is a bisphenol having a total of at least two acryloyl groups and/or methacryloyl groups per molecule The curable composition according to claim 5. (7) The compound [c] having at least two reactive unsaturated bonds per molecule is an isocyanuric acid derivative having a total of at least two acryloyl groups and/or methacryloyl groups per molecule. A curable composition according to claim 5. (8) The compound [c] having at least two reactive unsaturated bonds per molecule has a total of at least two acryloyl groups and/or methacryloyl groups per molecule, and at least one triazine ring. 6. The curable composition according to claim 5, which is a compound having the following properties.