JP2003192709A - Monomer composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monomer composition which can be restrained from color change and viscosity change caused by aging thermal deterioration with time and can keep radical polymerizability, and the polymerized material transparent and colorless. <P>SOLUTION: The monomer composition for a transparent material comprises at least one selected from styrene, a nucleus halogen-substituted styrene, a nucleus alkyl-substituted styrene, α-methylstyrene, 2,4-diphenyl-4-methyl-1-pentene and divinylbenzene, a monomer having one or more (meth)acryl groups and a stannum additive and/or a phosphorus additive. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a styryl group or α
A monomer composition containing a monomer having a methylstyryl group and a monomer having a (meth) acryl group, capable of suppressing color change and viscosity change caused by deterioration of heat with time, radicals The present invention relates to a monomer composition capable of maintaining the polymerizability and the colorless transparency of the material after polymerization. Furthermore, it relates to a transparent material obtained by polymerizing the same.

[0002]

Conventionally, styrene, nuclear halogen-substituted styrene, nuclear alkyl-substituted styrene, α-methylstyrene,
Radical polymerizable monomers such as 2,4-diphenyl-4-methyl-1-pentene and divinylbenzene are well known as raw materials for vinyl polymers, but when stored for a long period of time, light and Deterioration proceeds due to oxygen and the like, which causes coloring and formation of oligomers. Therefore, as a method for preventing polymerization, it is usually effective to add a polymerization inhibitor such as pt-butylcatechol, coexist with dissolved oxygen, or store at 25 ° C. or lower at low temperature. Further, as a method for preventing coloring, an air seal in refrigeration or a seal with an inert gas at room temperature is effective.

Further, methyl (meth) acrylate (means methyl methacrylate or methyl acrylate; hereinafter the same), ethyl (meth) acrylate, 2
-(Meth) acrylic acid ester such as hydroxyethyl (meth) acrylate and benzyl (meth) acrylate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane and tri The polymerizable monomer having two or more (meth) acryl groups (meaning methacryl groups or acryl groups. The same applies hereinafter) such as methylolpropane tri (meth) acrylate is
It is well known as a raw material for vinyl polymers in fields where transparency and light resistance are important. However, even when these monomers are stored for a long period of time, deterioration due to light, oxygen, etc. may occur, resulting in coloring and oligomers. There is a problem that causes the generation of.
Therefore, a polymerization inhibitor such as hydroquinone or p-methoxyphenol or an oxidation stabilizer such as di-t-butylphenol or t-butylcresol is usually added as a method for preventing the polymerization of a monomer having a (meth) acrylic group. The method, the coexistence of dissolved oxygen, and the low temperature storage at 20 ° C. or less are effective, and these methods have been put to practical use. Further, for prevention of coloration, addition of the above-mentioned oxidation stabilizer and sealing with an inert gas are effective.

However, styrene, nuclear halogen-substituted styrene, nuclear alkyl-substituted styrene, α-methylstyrene, 2,4-diphenyl-4-methyl-1-pentene,
In a composition in which a monomer having a styryl group such as divinylbenzene or an α-methylstyryl group as a polymerization group and a monomer having a (meth) acrylic group as a polymerization group coexist, mutual effects of the monomers occur, Deterioration easily occurs due to light, heat, oxygen and the like, and yellowing, thickening due to polymerization and gelation are observed in the conventional method. In addition, this deteriorated monomer is
If the polymerization is carried out as it is, there arises a problem that the polymer is colored and the homogeneity is deteriorated. Therefore, as a method for improving these, storage at a lower temperature of 10 ° C. or lower can be mentioned, but in this case, special equipment such as a low-temperature storage and a transport container is required, and the temperature is returned from the low temperature to the operating temperature. In that case, there was a problem in terms of manufacturing cost and product stability, such as the need for heating equipment and the easy inclusion of water in the composition.

Further, a monomer having a styryl group or an α-methylstyryl group as a polymerization group and a monomer having a (meth) acrylic group as a polymerization group are used as a raw material for a transparent material (see, for example, Japanese Patent Application Laid-Open Publication No. 2000-242242). JP-A-55-13747), it has been desired to develop a monomer composition in which a polymer has excellent physical properties as a transparent material and can be stored for a long period of time.

[0006]

An object of the present invention is to provide a monomer composition containing a monomer having a styryl group or an α-methylstyryl group and a monomer having a (meth) acrylic group. Another object of the present invention is to provide a monomer composition which can suppress deterioration due to light, heat, oxygen and the like and change over time, and can maintain the radical polymerizability of the monomer composition and the performance of the polymer. Further, it is another object of the present invention to provide a monomer composition in which a polymer has excellent physical properties as a transparent material even when polymerized after storage for a long period of time, and a transparent material which is a polymer thereof.

[0007]

A first invention is a monomer having a styryl group or an α-methylstyryl group, a monomer having at least one (meth) acrylic group, a tin-based additive, and And / or a stable monomer composition containing a phosphorus-based additive. The second invention is styrene, nuclear halogen-substituted styrene, nuclear alkyl-substituted styrene, α-methylstyrene,
One or more monomers selected from 2,4-diphenyl-4-methyl-1-pentene and divinylbenzene, a monomer having one or more (meth) acrylic groups, and a tin-based additive And / or a phosphorus-based additive, which is a monomer composition for a transparent material. A third invention is a monomer composition which further comprises an antioxidant and / or a polymerization inhibitor in the monomer composition of the first or second invention. 4th invention is 1st-3rd.
It is a transparent material obtained by radically polymerizing the monomer composition according to any one of the present inventions.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The first component in the monomer composition of the present invention is a monomer having a styryl group or an α-methylstyryl group, and specifically, for example, styrene, nuclear halogen-substituted styrene, It is one kind or a mixture of two or more kinds selected from nuclear alkyl-substituted styrene, α-methylstyrene, 2,4-diphenyl-4-methyl-1-pentene, divinylbenzene and the like. As a raw material of the transparent material, styrene, nuclear halogen-substituted styrene, nuclear alkyl-substituted styrene, α-methylstyrene, 2,4-diphenyl-4-methyl-1-pentene, and divinylbenzene are preferable. The proportion of the first component in the monomer composition can be selected in any range, but is usually 0.5 to 90% by weight, preferably 1 to 80% by weight. In the range of more than 90% by weight and less than 0.5% by weight, the effect of adding the tin-based additive and / or the phosphorus-based additive is not remarkable. When used as a raw material of a transparent material, the first component is preferably in the range of 1 to 80% by weight.

The second component in the monomer composition of the present invention is a polymerizable monomer having a (meth) acryl group, that is, an acryl group or a methacryl group, and one (meth) acryl group is contained in one molecule. There is no particular limitation as long as it is a compound having the above. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, i-butyl (meth) acrylate, n-hexyl (meth) acrylate. , 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glyceroyl mono (meth) acrylate, glycidyl (meth) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, methoxyethoxyethyl (meth) acrylate Triethylene glycol mono (meth) acrylate, methoxytriethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypropylene glycol (meth) acrylate, etc. Examples thereof include one kind or a mixture of two or more kinds of monomers having one (meth) acrylic group, and various properties such as high heat resistance, mechanical strength and durability are imparted to the polymer at the time of polymerization. For the purpose (meta)
It is more preferable to include a polyfunctional monomer having two or more acrylic groups.

Specific examples of the polyfunctional monomer include:
For example, one or a mixture of two or more of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate may be used. A polyfunctional monomer having an aromatic ring is also effective for the purpose of improving various properties such as the refractive index and mechanical strength of the polymer during the polymerization. For example, 2,2-bis (4-
(Meth) acryloxyethoxyphenyl) propane,
2,2-bis [4- (2- (meth) acryloxyethoxy) ethoxyphenyl] propane, 2,2-bis [4-
(2- (meth) acryloxyethoxy) diethoxyphenyl] propane, 2,2-bis [4- (2- (meth) acryloxyethoxy) triethoxyphenyl] propane, 2,2-bis [4- (2 -(Meth) acryloxyethoxy) tetraethoxyphenyl] propane, 2,2-
Bis [4-((meth) acryloxyethoxy) polyethoxyphenyl] propane, 2,2-bis [4- (2-
(Meth) acryloxyethoxycarbonyloxy) phenyl] propane, 2,2-bis {4-[(2- (meth)]
Examples thereof include one kind or a mixture of two or more kinds such as acryloxyethoxy) ethoxycarbonyloxy] phenyl} propane.

Furthermore, in order to adjust heat resistance and hardness, a monomer having three or more (meth) acrylic groups can be used. For example, various urethane-based poly (meth) acrylates and trimethylolpropane tri (meth) can be used. ) Acrylate is mentioned. The monomer having the (meth) acrylic group may be used alone or in a mixture of two or more kinds. The monomer having a (meth) acrylic group has a certain degree of stability by itself, but when mixed with the first component, the stability is significantly reduced.

The ratio of the (meth) acrylic group-containing monomer in the monomer composition can be selected in any range, but is usually 99.5 to 10% by weight, preferably 99 to
It is in the range of 20% by weight. In the range of more than 99.5% by weight and less than 10% by weight, the effect of adding the tin-based additive and / or the phosphorus-based additive is not significant. When used as a raw material for a transparent material, the second component is preferably in the range of 99 to 20% by weight.

In the monomer composition of the present invention, one or two of the above-mentioned monomers having a styryl group or α-methylstyryl group and a polymerizable monomer having at least one (meth) acrylic group are used. Mixtures of more than one are used, but other monomers can optionally be included. Other monomers include vinyl naphthalene, diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, (meth) acrylic acid amide, N, N-dimethylacrylamide, vinyl acetate, ethyl vinyl ether, butyl vinyl ether,
Vinyl monomers such as acrylonitrile and methacrylonitrile, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, isocyanate ethyl methacrylate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, m-xylene diisocyanate , M-tetramethylxylene diisocyanate, isophorone diisocyanate, and other isocyanate compounds may be included, and one or more mixed monomers thereof may be used.

When a tin-based additive is used in the present invention,
It is possible to prevent yellowing caused by deterioration of the monomer composition of the present invention, thickening and gelation due to polymerization, and to maintain radical polymerizability and various properties of the polymer. Specific examples of the tin-based additive include tetrabutyl tin,
Dibutyltin dilaurate, dibutyltin malate, dibutyltin dimaleate, dibutyltin dioleyl maleate, dibutyltin dioctyl maleate, dibutyltin dioctyl thioglycolate, dibutyltin oxide, 2
—Tin ethylhexanoate, dibutyltin dichloride, dioctyltin dilaurate, tin oxide, and one or a mixture of two or more thereof. The addition amount of the tin-based additive is usually 10 to 50000 ppm in the monomer composition of the present invention,
It is preferably in the range of 50 to 30,000 ppm. 10
If it is less than ppm, the effect of the tin-based additive is insufficient, and if it exceeds 50,000 ppm, curing failure occurs.

When a phosphorus-based additive is used in the present invention,
It is possible to prevent deterioration of the monomer composition of the present invention, particularly yellowing caused by polymerization, and to maintain radical polymerizability and various properties of the polymer. Specific examples of the phosphorus-based additive include triphenyl phosphite, diphenyl decyl phosphite, tridecyl phenyl phosphite, trioctyl phosphite, trioctadodecyl phosphite, trinonyl phenyl phosphite,
Triethyl phosphite, tributyl phosphite, tridodecyl trithiophosphite, tri (2,4-di-
Phosphorous acid esters such as t-butylphenyl) phosphate; phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-chloroethyl phosphate; di-2-ethylhexyl phosphate, methyl acid phosphate, ethyl Examples thereof include one kind or a mixture of two or more kinds of acidic phosphoric acid esters such as acid phosphate, propyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, and decyl acid phosphate.

The amount of the phosphorus-based additive added is usually 10 to 50000 ppm, preferably 5 in the monomer composition of the present invention.
It is in the range of 0 to 30,000 ppm. If it is less than 10 ppm, the effect due to the addition of the phosphorus-based additive is insufficient,
If it exceeds 000 ppm, curing failure will occur. In the present invention, the tin-based additive and the phosphorus-based additive may be used in combination.

In the present invention, when an antioxidant is further added, yellowing of the monomer composition, thickening due to polymerization and gelation can be further suppressed, and radical polymerization property and various properties of the polymer can be improved. Can be maintained. Specific examples of the antioxidant include 2,6-di-t-butyl-p.
-Phenol, 2,6-di-t-butyl-4-ethylphenol, butylated hydroxyanisole and other monophenol compounds; 2,2'-methylenebis (4-methyl-)
6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4 '
-Thiobis (3-methyl-6-t-butylpheno-
), 4,4'-butylidene bis (3-methyl-6-t
-Butylphenol) and other bisphenol compounds; dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,
Examples thereof include sulfur compounds such as 3'-thiodipropionate. These can be used alone or as a mixture of two or more.

The amount of the antioxidant added is in the range of usually 10 to 20,000 ppm, preferably 50 to 10,000 ppm in the monomer composition of the present invention. If it is less than 10 ppm, the effect due to the addition of the antioxidant is not sufficient.
If it exceeds 000 ppm, curing failure may occur.

In the present invention, when a polymerization inhibitor is further added, it is caused by deterioration of the monomer composition of the present invention.
In particular, it is possible to further suppress thickening and gelation due to polymerization. Specific examples of the polymerization inhibitor include compounds such as methoxyphenol, hydroquinone, and t-butylcatechol. These can be used alone or as a mixture of two or more. The amount of the antioxidant added is usually 10 to 20000 in the monomer composition of the present invention.
ppm, preferably in the range of 50 to 10,000 ppm. If it is less than 10 ppm, the effect of the polymerization inhibitor is insufficient, and if it exceeds 20000 ppm, curing failure may occur.

The monomer composition of the present invention can be obtained by stirring and mixing the above-mentioned monomer and various additives in the temperature range of 10 to 60 ° C. for 10 to 60 minutes. The composition obtained does not change even when stored at 60 ° C. or higher for 1 month. The transparent material of the present invention can be obtained by adding a radical polymerization initiator to the above-mentioned monomer composition and then curing it by a heat polymerization method or an active energy ray polymerization method.

The radical polymerization initiator is used to cure vinyl monomers, and examples thereof include benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate and t-. Butyl peroxypivalate, t-
Butyl peroxy neodecanoate, t-butyl peroxydiisobutyrate, azobisisobutyronitrile,
Azobis dimethyl valeronitrile etc. are mentioned. These can be used alone or in combination of two or more.

The amount of the polymerization initiator added is 10
It is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 0 parts by weight. If the amount is less than 0.01 parts by weight, curing will be insufficient, and if the amount exceeds 10 parts by weight, uniform polymerization tends to be difficult. Further, in the monomer composition of the present invention, in addition to the above-mentioned components, an ultraviolet absorber, a colorant, a release agent, a surfactant, an additive such as an antibacterial agent may be used within a range that is usually used. it can.

The transparent material of the present invention is prepared by adding a radical polymerization initiator to the monomer composition, and then pouring it into a casting of a desired shape, such as metal, glass or plastic, and heating and curing. Then, it can be obtained by demolding.
After curing, it is a colorless or colored transparent resin. Further, by adding a radical polymerization initiator to the monomer composition, bulk polymerization,
It is also possible to obtain a polymer once by a known polymerization technique such as suspension polymerization, emulsion polymerization or solution polymerization, and then form it into a predetermined shape by a known molding technique such as melt molding or compression molding. As the polymerization conditions, the polymerization temperature is in the range of 30 to 100 ° C., preferably the temperature is raised in the temperature range, and the polymerization time is 5 to 72.
The time is preferably 10 to 36 hours.

As the transparent material of the present invention, the one obtained by the above method can be used as it is, but if necessary, a hard coat treatment for improving the surface hardness, and a disperse dye for imparting fashionability. It is also possible to carry out a coloring treatment by.

[0025]

EFFECT OF THE INVENTION Since the monomer composition of the present invention can suppress the change over time due to deterioration and the like, the stability of the quality of the monomer composition can be maintained at high temperature and over a long period of time, and the monomer composition It does not affect the radical polymerizability of the product and the performance of the polymer. Further, the polymer is excellent in transparency.

[0026]

EXAMPLES The present invention will be described in detail below in relation to Examples and Comparative Examples, but the present invention is not limited to these. The abbreviations in the table are as follows. MMA; methyl methacrylate, MAEG; methoxyethyl methacrylate DM-2E; diethylene glycol dimethacrylate,
BPE-2A; 2,2-bis (4-acryloxyethoxyphenyl) propane, BPE-2M; 2,2-bis (4-methacryloxyethoxyphenyl) propane, S
t; styrene, MSt; α-methylstyrene, MSD;
2,4-diphenyl-4-methyl-1-pentene, DV
B: divinylbenzene, DBSL: dibutyltin dilaurate, DBSM: dibutyltin malate, TPP: triphenyl phosphite, TMP: trimethyl phosphate, BHT; 2,6-di-t-butyl-p-creso-
, MQ; methoxyphenol, TBC; t-butylcatechol.

The physical properties of the monomer composition were evaluated by the following measuring methods. (1) Viscosity: JIS K-2283, (2) Hue: JIS K-4101, (3) Acid value: JIS K-2501. The performance of the obtained resin plate was evaluated by the following test methods. (1) Light transmittance Transmittance Photometer (manufactured by Nippon Denshoku Industries Co., Ltd.)
The light transmittance of the test plate was measured according to K 7105. (2) Refractive index and Abbe number A 1 cm × 1.5 cm test piece was cut out from a cured resin plate and measured at 25 ° C. using an Abbe refractometer (DR-M2 manufactured by Atago Co., Ltd.).

Examples 1 to 8 100 g of each monomer composition shown in Table 1 was stirred and mixed at a temperature of 25 ° C. for 15 minutes, put into a glass sample bottle, and left in a constant temperature bath at 60 ° C. for 1 month. . The physical properties of each of the monomer compositions after warm storage were measured, and the monomer composition 20 was used.
0.4 g of t-butyl peroxy neodecanoate
The mixture was added, stirred and mixed, and this was poured into a casting mold composed of two glass disks having a diameter of 7 cm and a gasket made of ethylene-propylene rubber having a thickness of 2 mm. Then, in a hot air bath with a program temperature controller
The temperature was raised to 00 ° C over 18 hours, then maintained at 100 ° C for 2 hours, and then cooled down to 40 ° C over 2 hours. After curing, the demolded disk-shaped resin was annealed at 100 ° C. for another 2 hours. The polymer was measured for its optical properties. The results are shown in Table 1.

Comparative Examples 1 to 8 Tin-based additives for each of the monomer compositions shown in Table 1,
A stability test was conducted in the same manner as in Examples 1 to 8 except that the phosphorus-based additive was not included. Polymerization and evaluation of the physical properties of the polymer were carried out only for those which had little or no change in the physical properties of the monomer composition after warm storage. The results are shown in Table 2.

[0030]

[Table 1]

[0031]

[Table 2]

Each of the monomer compositions of Examples has excellent thermal stability as compared with Comparative Examples and has a property of being less susceptible to change over a long period of time. It was confirmed that there was almost no effect.

Claims (4)

[Claims] 1. A stable composition containing a monomer having a styryl group or an α-methylstyryl group, a monomer having at least one (meth) acrylic group, and a tin-based additive and / or a phosphorus-based additive. Monomer composition. 2. Styrene, nuclear halogen-substituted styrene, nuclear alkyl-substituted styrene, α-methylstyrene, 2,4-
One or more monomers selected from diphenyl-4-methyl-1-pentene and divinylbenzene, monomers having one or more (meth) acrylic groups, and tin-based additives and / or phosphorus. A monomer composition for a transparent material, which comprises a system additive. 3. A monomer composition which further comprises an antioxidant and / or a polymerization inhibitor in addition to the monomer composition according to claim 1 or 2. 4. A transparent material obtained by radical polymerization of the monomer composition according to claim 1.