JPH02208309A - Thiocarboxylic acid ester composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polymerizable thiocarboxylic acid ester composition which is particularly useful as an optical material and is also useful in paints, inks, adhesives, photosensitive resins, etc. It is something.

[Prior Art and Problems to be Solved by the Invention] Conventionally, various studies have been conducted on synthetic resins to replace inorganic glass, and there are many drawbacks, and no one with fully satisfactory properties has yet been obtained. For example, polymers obtained by polymerizing monomers whose main components are methyl methacrylate-1 and ethylene glycol bis(allyl carbonate) are used as optical resins and lenses, but their refractive index is approximately It is as low as 1.50.

For this reason, various crosslinkable monomers for high refractive index resins have been proposed. For example, resins containing a large number of halogen atoms, such as phenyl methacrylate, in which phenyl groups are substituted with halogen atoms, have been proposed in JP-A-61-28901. In addition, α-
A composition for a high refractive index resin containing naphthyl methacrylate as a main component has been proposed. Most of these monomers for high refractive index resins are solid at room temperature because they contain halogen atoms and condensed aromatic rings. Therefore, these monomers are dissolved in a liquid monomer at room temperature and polymerized.

Examples of the above liquid monomer include the following formula CH.

Methacrylic acid esters represented by CH2=C-C0CH2CI (2SR'(R' represents an argyl group)) are known.

However, a resin made by polymerizing this monomer does not have a very high refractive index.

[Means to solve the problem]

Therefore, the present inventors have developed a jn-mer that is liquid at room temperature and is suitable for dissolving monomers that are solid at room temperature for high refractive index resins.
Research has been conducted with the aim of developing monomers that provide resins with high refractive index and low dispersion, and excellent transparency, impact resistance, weather resistance, and light weight. As a result, a novel thiocarboxylic acid ester compound having a specific structure is a monomer that achieves the above object, and a mixture of the ten thiocarboxylic acid ester compounds and a monomer having two or more polymerizable groups is polymerized. It has been discovered that by doing so, a resin that achieves the above-mentioned objectives can be obtained, and the present invention has been completed.

That is, the present invention provides (δ) general formula [l] CH,, =(, C3(CHCH3)n+R' (
J) 100 parts by weight of a thiocarboxylic acid ester compound represented by R2R3 (b) A monomer having two or more polymerizable groups that can be copolymerized with the above thiocarboxylic acid ester compound
This is a thiocarboxylic acid ester composition characterized by comprising 20 to 500 parts by weight.

The thiocarboxylic acid ester compound represented by the above general formula [I] is a new compound.

In the general formula CI), R2 and R1 may each be the same or different hydrogen atoms or bar groups, but from the viewpoint of using the polymer obtained by polymerization as an optical+A material, , a hydrogen atom or a methyl group.

In the general formula CI), R4 is a substituted or unsubstituted Hensyl group.

A halogen atom is suitable as a substituent for the Hensyl group represented by R4 above.

Furthermore, in the above general formula CI), m may be an integer of 1 or more. Generally, as the value of m increases, the content of sulfur per molecule increases, so that the refractive index of the resin obtained by polymerization increases JiQ and the impact resistance also improves. However, if m is made too large, the viscosity of the compound represented by the general formula [I] will increase rapidly, making it difficult to handle and causing problems such as the heat resistance of the resin obtained by polymerization being impaired. It's coming. Therefore, considering the refractive index, surface 4-way impact resistance, and heat resistance of the resulting resin, m is 1
It is preferable to select it in the range of 1 to 5, particularly in the range of 1 to 3.

The thiocarboxylic acid ester compound represented by the above general formula used in the present invention can be identified and confirmed by the following means.

(a) By measuring the infrared absorption spectrum (JR), 315 (absorption based on CH bonds at 1 to 2800 cm-', absorption based on terminal double bonds at 1650 to 1620 cm-', A strong absorption of the carbonyl group based on the 1,000 oni[stellate bond] is observed near -'.

(a)11]-Nuclear magnetic resonance spectrum ('H-NMR
), the compound can be easily identified. In particular, when R is Stell W in general formula [I], there is a peak based on the methyl group at around δ1.9 ppm, and a peak based on the terminal vinylideneprone at around 65.7 and δ6.1 ppm. 3 : ], : respectively.
A pattern characteristic of methacrylic acid esters is observed at a ratio of 1%. In addition, when R is a hydrogen atom, 65.6 to 7
Three hydrogen atoms are observed in ppm in a pattern peculiar to acrylic esters. Furthermore, in the dioether chain, the hydrogen on the carbon atom bonded to the sulfur atom is δ2,9
ppln4] shows a pattern of peaks corresponding to the binding state. Furthermore, when either R2 or R3 is a methyl group, a double line is observed near δ], 1 ppm. Furthermore, hydrogen at the Henschel position is 63.5 to 4.5 p
It is recognized in pm. Moreover, aromatic hydrogen is 67-68.
A peak is observed at 5 ppm.

If other hydrogen atoms are present, a spectral pattern corresponding to their convenience will be exhibited. The compound can be easily identified from the above information.

(1) Determine the weight percent of carbon, hydrogen, sulfur, and halogen through elemental analysis, and then calculate the weight percent of each recognized element.
By subtracting the sum from 100, the weight percent of oxygen can be calculated, and the compositional formula of the compound can be determined.

- The thiocarboxylic acid ester compound represented by the format [■] is represented by the following formula [■] R3(CI(CH3)mR' (I
I) It can be obtained by reacting a compound represented by R''R3 with a compound represented by the following formula [111].

The charging molar ratio of both raw materials is usually (-format (n, compound represented by 1)/(-format CIr1))
It may be selected from the range of -0.8 to 1.5, but it is preferable to use equal amounts.

In this reaction, hydrogen chloride is produced as a by-product. Generally, in order to remove this hydrogen chloride from the reaction system, it is preferable to coexist a base as a hydrogen chloride scavenger in the reaction system or to pass an inert gas such as nitrogen gas into the reaction system.

The base used as the hydrogen chloride scavenger is not particularly limited, and any known base can be used. Trialkylamines such as trimethylamine, 1-ethylamine, and tripropylamine; pyridine;
Examples include tetraster urea; sodium hydroxide; mono- to lium carbonate, and the like.

The amount of base used is preferably 1 mol or more per 1 mol of carboxylic acid chloride.

In the reaction in the present invention, it is generally preferable to use an organic solvent. Examples of solvents preferably used include aliphatic or aromatic hydrocarbons or halogenated hydrocarbons such as benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, and ethylene chloride. ; Ethers such as diethyl ether, dioxane, tetrahydrofuran, N, N
Examples include N,N-dialkylamides such as dimethylpolamide and N,N-diethylformamide; dister sulfoxide, and the like.

The temperature in the reaction can be selected from a wide range, generally from -20°C to 100°C, preferably from 0°C to 50°C.
You can choose from the range. The reaction time varies depending on the type of raw materials, but is usually 5 minutes to 24 hours, preferably 10 minutes to 4 hours.
You can choose from the time range.

Further, it is preferable to stir the reaction mixture during the reaction.

The method for isolating and purifying the target product, ie, the compound represented by -form (N) from the reaction system, is not particularly limited, and any known method can be employed.

The thiocarboxylic acid ester compound used in the present invention and represented by the general formula N'l is a liquid monomer that has a high refractive index, low dispersion, is colorless and transparent, has a small specific gravity, and has excellent impact resistance. Gives union.

Next, the other component of the thiocarboxylic acid ester 3:INN animal of the present invention is a monomer having two or more polymerizable groups that can be copolymerized with the above-mentioned thiocarboxylic acid ester compound. Since the above-mentioned thiocarboxylic acid ester compound is liquid at room temperature, the above-mentioned monomer having three or more polymerizable groups can be well mixed even if it is solid.

Specific examples of the above monomers include ethylene glycol diacrylate-1, diethylene glycol dimethacrylate-1, ethylene glycol bisgelicidyl methacrylate, and bisphenol A dimethacrylate-1.
, 2,2,6,6-titrabromobisphenol A dimethacryle-1-2,2bis(4-methacryloyloxyethoxyphenyl)propane, 2,2-his(3,5-
dizolomo-4,-meta/”Jroiluoni1-siei-=
Acrylic acid and methacrylic acid ester compounds such as I-diphenyl)propane; diallyl phthalate-1, diallyl terephthalate, diallyl isophthalate-1, diallyl tartrate, diallyl epoxysuccinate, diallyl maleate, sialyl chlorate, diallyl hexapthalate, Diallyl carbonate 1, allyl diglycol carbonate
These are allyl compounds such as 1. These i-mers can be used alone or in combination of two or more.

The mixing ratio of these copolymerizable monomers to the thiocarboxylic acid ester compound represented by general formula (1) is 20 to 500 parts by weight of the copolymerizable monomer to 100 polymerized parts of the thiocarboxylic acid ester compound. and more preferably 20 to 200 parts by weight.

In the present invention, further unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid;
Methyl acrylate, methyl methacrylate, methyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, trifluoromethyl methacrylate-1~
Acrylic acid and methacrylic acid ester compounds such as; fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, diphenyl fumarate; allyl cinnamate,
Allyl compounds such as allyl isocyanate; aromatic vinyl compounds such as styrene, chlorostyrene, methylstyrene, hinylnaphthalene, isopropenylnaphculene, bromostyrene, and dipromostyrene may also be used in combination.

The polymerization method for obtaining a polymer from the thiocarboxylic acid ester composition of the present invention is not particularly limited, and any known radical polymerization method can be employed. Polymerization initiation means include the use of radical polymerization initiators such as various peroxides and azo compounds, or ultraviolet light,
This can be carried out by irradiation with α-rays, β-rays, T-rays, etc., or a combination of both.

To illustrate a typical polymerization method, the monomer composition of the present invention containing a radical polymerization initiator is injected between molds held by an elastomer gasket or spacer, cured in an air oven, and then taken out. Cast polymerization is used.

The radical polymerization initiator is not particularly limited and any known one can be used, but representative examples include penzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, and lauroyl peroxide. , acetyl peroxide; t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate
Peroxy esters such as 1.; percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhegysilyl oxydicarbonate, di-sec butyl peroxydicarbonate; azo compounds such as azuhisisobutyronitrile; . The amount of the radical polymerization initiator used varies depending on the polymerization conditions, the type of initiator, and the composition of the monomers mentioned above, and cannot be generally limited, but is generally 0.00 parts by weight per 100 parts by weight of the total monomers. It is suitable to use it in a range of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight.

Polymerization conditions, particularly temperature, affect the properties of the resulting high refractive index resin. This temperature condition is affected by the type and amount of initiator and the type of monomer, so - although it cannot be generalized - polymerization starts at a relatively low temperature in boat fishing, and the temperature can be slowly increased. It is preferable to carry out so-called tapered two-stage polymerization, in which the polymer is cured at high temperature at the end of the polymerization.

Polymerization time, like temperature, also varies depending on various factors, so it is best to determine the optimal time according to these conditions in advance, but in general, conditions should be set so that polymerization is completed in 2 to 40 hours. is preferred.

Of course, during the polymerization, various stabilizers and additives such as release agents, ultraviolet absorbers, antioxidants, color inhibitors, antistatic agents, fluorescent dyes, dyes, and pigments may be selected as necessary. It can be used.

Furthermore, the high refractive index resin obtained by the above method can be subjected to the following treatments depending on its use. That is, dyeing using dyes such as disperse dyes, vertcoating agents whose main components are silane coupling agents and sols of oxides such as silicon, zirconium, antimony, and aluminum, and dyeing which uses organic polymers as their main components. Hard coating treatment with hard coating agent, SiO□, TjOz, ZrO
Processing such as anti-fouling treatment, antistatic treatment, etc. by vapor deposition of a thin film of metal oxide, coating of a thin film of organic polymer, etc.
It is also possible to perform subsequent processing.

〔effect〕

The thiocarboxylic acid ester compound, which is one component of the composition of the present invention, is liquid at room temperature and can be suitably used as a monomer for melting a high refractive index resin monomer that is solid at room temperature.

In addition, the polymer obtained by polymerizing the thiocarboxylic acid ester composition of the present invention has excellent impact resistance and weather resistance, and further has a refractive index of 1.57 or more, low dispersion, transparency,
Excellent lightweight. Therefore, the high refractive index resin obtained by polymerizing the thiocarboxylic acid ester composition of the present invention is useful as an organic glass, and is suitable for optical lenses such as eyeglass lenses and optical equipment lenses. It can be suitably used for applications such as disk substrates and optical fibers.

〔Example〕

EXAMPLES Hereinafter, in order to specifically explain the present invention, Examples will be given and explained, but the present invention is not limited to these Examples.

The thiocarboxylic acid ester compound obtained in the present invention was identified by the following analysis method.

(Using IITR Spec I R-4,4,0 model manufactured by Shimadzu Corporation, the sample was sandwiched between KBr plates and measured in a thin film state.

(2)'H-NMR spectrum Using PMX-60SI type (60 MHz) manufactured by JEOL Ltd., the sample was diluted to CDCβ3 and measured using tetramethylsilane as an internal standard.

(3) Elemental analysis ■ Carbon and hydrogen were analyzed using a CHN coder MT-2 manufactured by Yanagimoto Seisakusho, and sulfur was measured using a flask combustion method.

(4) Refractive index (ηD') At 20°C using an Asohe refractometer (model 3T) manufactured by Atago ■.
The refractive index was measured.

Further, various physical properties of the high refractive index resins obtained in Examples were measured by the following test methods.

(1) Refractive index (η, zo), Atsube number (ν) The refractive index and Atsube number at 20°C were measured using an Asohe refractometer (Model 3T) manufactured by Atago ■. Brosenaphthalene was used as a contact liquid.

(2) Appearance Judgment was made visually.

(3) Place the sample in a long-life xenon fade meter (FAC-25AX-HC type) made by Weather Resistance Suga Test Instruments 01,
After being exposed to xenon light for 100 hours, the degree of coloring of the sample was visually observed, and samples with a lower degree of coloring than polystyrene were evaluated with ○, those with the same degree of coloring were △, and those with high coloring were evaluated with ×.

(4) Impact resistance 127 mm on a disk-shaped sample plate with a thickness of 21 m and a diameter of 65 m11
A steel ball of a predetermined weight was allowed to fall naturally from a height of 1.5 cm, and the weight of the steel ball that would not damage the sample plate was measured. The results were evaluated as A to E according to the criteria shown in Table 1.

Table 1 (5) Adhesion of Bartco-1/Membrane After thoroughly washing a plate-shaped resin sample with methanol and air drying it to a clear state, it was diluted with 10% 1-lium hydroxide aqueous solution. Soaked for minutes.

The sample was then pretreated by washing with water and drying.

On the other hand, in advance, 1.20 parts by weight of bis(T-triethoxysilylprobyl) carbonate, 10 parts by weight of γ-glycidoxyprobyl trime to xysilane, and 30 parts of colloidal silica (methanol sol manufactured by Nissan Chemical Co., Ltd.) were placed. , 30 parts by weight of methyl cellosolve, 10 parts by weight of 0.05N hydrochloric acid, and 0.25 parts by weight of ammonium perchlorate were thoroughly mixed to prepare a hard coat liquid. The pretreated sample was immersed in this hard coat solution, and after thoroughly air-dried at room temperature,
The coating was cured by heating at C for 3 hours. The adhesion of the obtained film was evaluated by the following test method. After making 100 squares of l + + + i
Then, when the film was quickly peeled off, the state of peeling of the film was visually observed and evaluated by the number of squares that remained without peeling out of 100 squares.

In addition, some of the monomers used in the following examples are represented by the following symbols. However, the number in [ ] is the refractive index of the homopolymer.

BDMA: 2 2' 6 6'-tetrabromobisphenol A dimethacrylate C1,604,) BBMEPP: 2,2-bis(3,5-dibromo-4-
methacryloyloxyethoxyphenyl)propyne (1,600) BMEPP: 2
．． 2-bis(4-methacryl 1'yloxyethoxyphenyl)propane (1,558) DEGM diethylene glycol dimethacrylate (1
, 508) Production Example 1 20.2 g of 2-benzylthioethyl 1,000 ol (0
, L 1mo) and triedylemine 13.3 g (
0.13 moβ) and 100 mβ of anhydrous chloroporum were charged and cooled to 0°C. While stirring, 12.6 g (0.12 mo#) of methacrylic acid chloride was gradually added dropwise. At this time, the reaction temperature was maintained at 0 to 5°C, and after the dropwise addition was completed, the mixture was further stirred at 20"C for 1 hour.

Thereafter, the reaction mixture was poured into water, and the organic layer was washed with a dilute sodium carbonate aqueous solution and then with water.

The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained oil was distilled under reduced pressure to obtain 16.3 g of the desired 2-pendylthioethyl thiomethacrylate as a colorless transparent liquid with a boiling point of 132 to 135°C (0.05 O, 5 mm 1 L). The ratio was 1.584.1670 in the IR spectrum
A strong carbonyl group was observed at cm-', and an absorption based on a terminal double bond was observed at 1640 cm-'.

In addition, in 'H-NMR (CD (in solvent 13, based on tetramethylsilane, ppm), three peaks derived from the hydrogen (c) of the methyl group were found at 61.93 with a coupling constant of 211.
As a doublet of z, four peaks derived from methylene group hydrogen (d) and (e) are present at δ2.4 to δ3.3 as a multiplet, and hydrogen at the Henschel position (f) is at 63.76. Two peaks derived from the hydrogen (a) of the vinyl group appear as a single line around 65.56, a multiplet peak around 66.06 originates from the hydrogen (b) of the vinyl group. One peak derived from δ7.1 was observed as a multiplet, and five peaks derived from hydrogen (g) of the phenyl group were observed as a multiplet near δ7.1.

After washing the organic layer with a water solution, the organic layer was washed with water.

The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained oil was purified by column chromatography (filling material: Nisilica gel, developing agent: chloroform), and the elemental analysis value (the value in parentheses is a calculated value) was obtained by the following formula: C:
61.81% (61,86χ), T(: 6.09%(
6,39χ), S: 25.33% (25,4]χ), which agreed well with the calculated value.

Production Example 2 19.8 g of 2-hensylthiopropane-1-thiol was added to a three-loaf flask equipped with a thermometer, stirrer, and dropping funnel.
g (0,10moβ) and triethylamine 11,1
g (0.11mo4) in 100m of anhydrous chloroform!
was charged and cooled to 0°C. While stirring, 11.5 g (0.11 mon) of methacrylic acid chloride was gradually added dropwise. At this time, the reaction temperature was maintained at 0 to 5°C, and after the dropwise addition was completed, the mixture was further stirred at 20°C for 1 hour.

Thereafter, the reaction mixture was poured into water to obtain a compound represented by dilute carbonic acid 1-IJ as a colorless and transparent oil.

This material had a refractive index of 1.580. In addition, strong absorption based on carbonyl group was observed at 1670 cm-' in the IR spectrum. In addition, the elemental analysis value (() is the calculated value) is C: 61.56% (61,86χ
), H: 6.40% (6,39χ), S: 25.49
% (25, 11°16), which was in good agreement with the calculated value.

Production Example 3 The following compound was obtained in exactly the same manner as Production Example 2, except that 2,4-dibromophenylmethylthioethylthiol and acrylic acid chloride were used as raw materials.

r This compound is a colorless transparent viscous liquid with a refractive index of 1.
It was 604. Also, in the IR spectrum, 167
Strong absorption based on carbonyl group was observed at 0 cm-'. The elemental analysis value (the values in parentheses are calculated values) is C:3
6.52% (36,38χ), H: 3.21% (3,
05X), S: 16.35Z (16,19Z), which agreed well with the calculated value.

Examples 1 to 7 To 100 parts by weight of the thiocarboxylic acid ester compounds produced in Production Examples 1 to 3, 1 part by weight of t-butylperoxy-2-ethylhexanate as a radical polymerization initiator was added and mixed well. The compounds shown in Table 2 as monomers having two or more polymerizable groups copolymerizable with the thiocarboxylic acid ester compound were mixed therein. This mixed solution was poured into a mold consisting of a glass plate and a gasket made of ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization is carried out at 30°C to 90°C using an air oven.
The temperature was gradually increased over 18 hours until it reached 90°C.
Holds time. After polymerization, remove the mold from the air furnace and
After cooling, the polymer was removed from the glass mold. Various physical properties of the obtained polymer were measured and shown in Table 2.

Comparative Examples 1-2 Methyl thiomethacrylate and methacrylic acid 2 as monomers
- The same procedure as in Example 1 was carried out except that methylthioethyl was used. Various physical properties of the obtained polymer are also listed in Table 2.

Reference Example The thiocarboxylic acid ester compounds obtained in Production Examples 1 to 3 were independently polymerized in the same manner as in Example 1. The physical properties of the obtained polymer are shown in Table 3.

Claims (1)

[Claims] (1) (a) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^1 is a hydrogen atom or a methyl group, and R^2 and R^3 are the same or different hydrogen atoms or alkyl groups, respectively. group, R^4 is a substituted or unsubstituted benzyl group, and m is a number of 1 or more. ] A thiocarboxylic acid characterized by comprising 100 parts by weight of a thiocarboxylic acid ester compound represented by the above and (b) 20 to 500 parts by weight of a monomer having two or more polymerizable groups that can be copolymerized with the above thiocarboxylic acid ester compound. Ester composition.