JP2009001658A - Triazine-based resin composition and molding made with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a triazine-based resin composition which has high heat resistance and a high refractive index and is useful in optical uses such as various plastic lenses and optical films and to provide a molding made with the triazine-based resin composition. <P>SOLUTION: The triazine-based resin composition is obtained by blending 100 parts weight triazine-based resin having a specific structure and 1,000-1,000,000 weight-average molecular weight, 0.001-2 parts weight of a phenol-based antioxidant and/or a phosphorus-based antioxidant and, further and preferably, a lactone-based stabilizer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has high transparency and a high refractive index, and is expected to be applied to various plastic lenses, prism sheets, transparent coating materials such as antireflection films and optical fiber coating materials, and optical materials such as optical films. The present invention relates to a triazine-based resin composition and a molded body comprising the same.

  In recent years, transparent heat-resistant resins have been used for lenses such as camera-equipped mobile phones and digital cameras because they are inexpensive and easy to mold. The transparent heat-resistant resin used for the lens is excellent in transparency, heat resistance and moldability, and is required to have a high refractive index. For example, as such a material, a cyclic olefin resin (see, for example, Non-Patent Document 1) is used. It can be mentioned as a representative example.

  Also, since resins used for optical materials are required to have excellent properties such as heat resistance depending on the use environment, methods for improving the properties of materials using various additives have been proposed. (For example, refer to Patent Document 1).

  As described above, the transparent heat-resistant resin used for the optical material has been developed and improved in various ways. However, due to the recent trend of reducing the weight and size of portable devices, a material having a higher refractive index is required. (For example, refer nonpatent literature 2.).

JP 09-268250 A Polyfile, September issue, p. 36-43 (2004) NIKKEI ELECTRONICS p. 79-85 (2004. 9.13)

  The present invention provides a triazine-based resin composition that solves the problems described above, has good heat resistance, and is useful for optical applications with a high refractive index, and a molded body and a film using the resin composition. It is for the purpose.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have formulated a triazine resin composition comprising a specific triazine resin and a phenolic antioxidant and / or a phosphorus antioxidant at a specific ratio. It has been found that the product is a resin composition having excellent transparency, heat resistance, and moldability and having a high refractive index, and the present invention has been completed.

  That is, the present invention comprises a phenol-based antioxidant and / or a phosphorus-based antioxidant with respect to 100 parts by weight of a triazine-based resin having a unit represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 1,000,000. The present invention relates to a triazine-based resin composition containing 0.001 to 2 parts by weight and a molded body made of the same.

（ここで、Ｘは窒素、酸素、硫黄であり、Ｒ_１は炭素数１〜２０のアルキル基、炭素数３〜２０の単環又は多環状のシクロアルキル基、炭素数７〜２０のアラルキル基、芳香族基、複素環化合物、シアノ基、チオシアノ基であり、そして炭素数１〜２０のアルキル基、炭素数３〜２０の単環又は多環状のシクロアルキル基、芳香族基、複素環化合物は窒素、酸素、硫黄を介してトリアジン環と結合していても良く、Ｒ_２は炭素数１〜２０の２価の脂肪族鎖、炭素数３〜２０の単環又は多環状の２価の脂肪族環，２価の芳香族環，２価の複素環、炭素数２〜２０のエーテル基、炭素数２〜２０のスルフィド基、炭素数２〜２０のスルホキシド基、炭素数２〜２０のスルホン基を示す。）
以下に、本発明を詳細に説明する。

(Here, X is nitrogen, oxygen, or sulfur, R ₁ is an alkyl group having 1 to 20 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. An aromatic group, a heterocyclic compound, a cyano group, a thiocyano group, and an alkyl group having 1 to 20 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms, an aromatic group, and a heterocyclic compound May be bonded to the triazine ring via nitrogen, oxygen or sulfur, and R ₂ is a divalent aliphatic chain having 1 to 20 carbon atoms, a monocyclic or polycyclic divalent divalent chain having 3 to 20 carbon atoms. Aliphatic ring, divalent aromatic ring, divalent heterocycle, C2-C20 ether group, C2-C20 sulfide group, C2-C20 sulfoxide group, C2-C20 Represents a sulfone group.)
The present invention is described in detail below.

The triazine-based resin composition of the present invention comprises a unit represented by the above general formula (1) and is composed of a triazine-based resin having a weight average molecular weight of 1,000 to 1,000,000. The weight average molecular weight here can be measured by gel permeation chromatography. X in the formula is nitrogen, oxygen, or sulfur, and R ₁ is an alkyl group having 1 to 20 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms, or an aralkyl having 7 to 20 carbon atoms. Groups, aromatic groups, heterocyclic compounds, cyano groups, thiocyano groups, and alkyl groups having 1 to 20 carbon atoms, monocyclic or polycyclic cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups, and heterocyclic rings The compound may be bonded to the triazine ring through nitrogen, oxygen, or sulfur, and R ₂ is a divalent aliphatic chain having 1 to 20 carbon atoms, a monocyclic or polycyclic divalent having 3 to 20 carbon atoms. Aliphatic ring, divalent aromatic ring, divalent heterocyclic ring, ether group having 2 to 20 carbon atoms, sulfide group having 2 to 20 carbon atoms, sulfoxide group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. Of the sulfone group.

R ₁ may be, for example, a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, or a dodecyl group; a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, dicyclopentadi A cycloalkyl group such as an enyl group; an aralkyl group such as a benzyl group; an aromatic group such as a phenyl group, a tolyl group and a naphthyl group; a heterocyclic compound group such as a thienyl group, a pyridyl group and a triazine compound; a cyano group; a thiocyano group; Examples of those bonded to the triazine ring through oxygen and sulfur include alkoxy groups such as methoxy group, ethoxy group, phenoxy group and cresyl group; sulfide groups such as thiomethyl group and thiophenoxy group; dimethylamino group, cyclohexylamino group, An amino group such as diphenylamino can be mentioned.

R ₂ is a divalent aliphatic chain such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an octylene group or a dodecylene group; a cyclopentylene group, a cyclohexylene group or a cyclooctylene group. Divalent aliphatic rings such as dicyclopentadienyl group; aralkyl groups such as benzyl group; divalent aromatic rings such as phenylene group, tolylene group, 2,2-diphenylpropane group and naphthylene group; thienylene group Divalent heterocyclic rings such as pyridyl group and triazine ring; ether groups such as dimethyl ether group and diphenyl ether group; sulfide groups such as dimethyl sulfide group and diphenyl sulfide group; sulfoxide groups such as dimethyl sulfoxide group; sulfones such as diphenyl sulfone group The group can be mentioned.

  And when it is a triazine-type resin whose weight average molecular weight is less than 1000, the obtained triazine-type resin composition becomes a very brittle thing. On the other hand, in the case of a triazine-based resin having a weight average molecular weight exceeding 1000000, the triazine-based resin composition obtained has a very high viscosity at the time of melting or dissolution, so that the handleability at the time of molding processing is inferior.

  As a method for producing the triazine resin, any production method may be used as long as the triazine resin can be produced. For example, the triazine compound represented by the following general formula (2) and the following general formula: It can be produced by polymerizing at least one of the compounds represented by (3).

（ここで、Ｙは塩素、臭素、沃素、−ＳＨであり、Ｒ_３は炭素数１〜２０のアルキル基、炭素数３〜２０の単環又は多環状のシクロアルキル基、炭素数７〜２０のアラルキル基、芳香族基、複素環化合物、シアノ基、チオシアノ基であり、そして炭素数１〜２０のアルキル基、炭素数３〜２０の単環又は多環状のシクロアルキル基、芳香族基、複素環化合物は窒素、酸素、硫黄を介してトリアジン環と結合していても良い。）

(Y is chlorine, bromine, iodine, or -SH, and R ₃ is an alkyl group having 1 to 20 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms, or 7 to 20 carbon atoms. An aralkyl group, an aromatic group, a heterocyclic compound, a cyano group, a thiocyano group, and an alkyl group having 1 to 20 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms, an aromatic group, The heterocyclic compound may be bonded to the triazine ring via nitrogen, oxygen, or sulfur.

（ここで、Ｚはそれぞれ塩素、臭素、沃素、−ＯＨ、−ＳＨであり、Ｒ_４は炭素数１〜２０の２価の脂肪族鎖、炭素数３〜２０の単環又は多環状の２価の脂肪族環，２価の芳香族環，２価の複素環、炭素数２〜２０のエーテル基、炭素数２〜２０のスルフィド基、炭素数２〜２０のスルホキシド基、炭素数２〜２０のスルホン基である。）
一般式（２）で表されるトリアジン化合物の具体的例示としては、例えば２−メチル−４，６−ジクロロ−ｓ−トリアジン、２−エチル−４，６−ジクロロ−ｓ−トリアジン、２−ドデシル−４，６−ジクロロ−ｓ−トリアジン、２−ベンジル−４，６−ジクロロ−ｓ−トリアジン、２−フェニル−４，６−ジクロロ−ｓ−トリアジン、２−ナフチル−４，６−ジクロロ−ｓ−トリアジン、２−メトキシ−４，６−ジクロロ−ｓ−トリアジン、２−エトキシ−４，６−ジクロロ−ｓ−トリアジン、２−フェノキシ−４，６−ジクロロ−ｓ−トリアジン、２−チオメチル−４，６−ジクロロ−ｓ−トリアジン、２−チオエチル−４，６−ジクロロ−ｓ−トリアジン、２−チオフェニル−４，６−ジクロロ−ｓ−トリアジン、２−ジメチルアミノ−４，６−ジクロロ−ｓ−トリアジン、２−シクロヘキシルアミノ−４，６−ジクロロ−ｓ−トリアジン、２−アニリノ−４，６−ジクロロ−ｓ−トリアジン、２−ヒドロキシ−４，６−ジクロロ−ｓ−トリアジン、２−シアノ−４，６−ジクロロ−ｓ−トリアジン、２−チオシアノ−４，６−ジクロロ−ｓ−トリアジン、２−（２−チエニル）−４，６−ジクロロ−ｓ−トリアジン、２−（４−ピリジル）−４，６−ジクロロ−ｓ−トリアジン、２−メチル−４，６−ジブロモ−ｓ−トリアジン、２−エチル−４，６−ジブロモ−ｓ−トリアジン、２−ドデシル−４，６−ジブロモ−ｓ−トリアジン、２−ベンジル−４，６−ジブロモ−ｓ−トリアジン、２−フェニル−４，６−ジブロモ−ｓ−トリアジン、２−ナフチル−４，６−ジブロモ−ｓ−トリアジン、２−メトキシ−４，６−ジブロモ−ｓ−トリアジン、２−エトキシ−４，６−ジブロモ−ｓ−トリアジン、２−フェノキシ−４，６−ジブロモ−ｓ−トリアジン、２−チオメチル−４，６−ジブロモ−ｓ−トリアジン、２−チオエチル−４，６−ジブロモ−ｓ−トリアジン、２−チオフェニル−４，６−ジブロモ−ｓ−トリアジン、２−ジメチルアミノ−４，６−ジブロモ−ｓ−トリアジン、２−シクロヘキシルアミノ−４，６−ジブロモ−ｓ−トリアジン、２−アニリノ−４，６−ジブロモ−ｓ−トリアジン、２−ヒドロキシ−４，６−ジブロモ−ｓ−トリアジン、２−シアノ−４，６−ジブロモ−ｓ−トリアジン、２−チオシアノ−４，６−ジブロモ−ｓ−トリアジン、２−（２−チエニル）−４，６−ジブロモ−ｓ−トリアジン、２−（４−ピリジル）−４，６−ジブロモ−ｓ−トリアジン、２−メチル−４，６−ジヨード−ｓ−トリアジン、２−エチル−４，６−ジヨード−ｓ−トリアジン、２−ドデシル−４，６−ジヨード−ｓ−トリアジン、２−ベンジル−４，６−ジヨード−ｓ−トリアジン、２−フェニル−４，６−ジヨード−ｓ−トリアジン、２−ナフチル−４，６−ジヨード−ｓ−トリアジン、２−メトキシ−４，６−ジヨード−ｓ−トリアジン、２−エトキシ−４，６−ジヨード−ｓ−トリアジン、２−フェノキシ−４，６−ジヨード−ｓ−トリアジン、２−チオメチル−４，６−ジヨード−ｓ−トリアジン、２−チオエチル−４，６−ジヨード−ｓ−トリアジン、２−チオフェニル−４，６−ジヨード−ｓ−トリアジン、２−ジメチルアミノ−４，６−ジヨード−ｓ−トリアジン、２−シクロヘキシルアミノ−４，６−ジヨード−ｓ−トリアジン、２−アニリノ−４，６−ジヨード−ｓ−トリアジン、２−シアノ−４，６−ジヨード−ｓ−トリアジン、２−チオシアノ−４，６−ジヨード−ｓ−トリアジン、２−（２−チエニル）−４，６−ジヨード−ｓ−トリアジン、２−（４−ピリジル）−４，６−ジヨード−ｓ−トリアジン、２−メチル−４，６−ジメルカプト−ｓ−トリアジン、２−エチル−４，６−ジメルカプト−ｓ−トリアジン、２−ドデシル−４，６−ジメルカプト−ｓ−トリアジン、２−ベンジル−４，６−ジメルカプト−ｓ−トリアジン、２−フェニル−４，６−ジメルカプト−ｓ−トリアジン、２−ナフチル−４，６−ジメルカプト−ｓ−トリアジン、２−メトキシ−４，６−ジメルカプト−ｓ−トリアジン、２−エトキシ−４，６−ジメルカプト−ｓ−トリアジン、２−フェノキシ−４，６−ジメルカプト−ｓ−トリアジン、２−チオメチル−４，６−ジメルカプト−ｓ−トリアジン、２−チオエチル−４，６−ジメルカプト−ｓ−トリアジン、２−チオフェニル−４，６−ジメルカプト−ｓ−トリアジン、２−ジメチルアミノ−４，６−ジメルカプト−ｓ−トリアジン、２−シクロヘキシルアミノ−４，６−ジメルカプト−ｓ−トリアジン、２−アニリノ−４，６−ジメルカプト−ｓ−トリアジン、２−メルカプト−４，６−ジメルカプト−ｓ−トリアジン、２−シアノ−４，６−ジメルカプト−ｓ−トリアジン、２−チオシアノ−４，６−ジメルカプト−ｓ−トリアジン、２−（２−チエニル）−４，６−ジメルカプト−ｓ−トリアジン、２−（４−ピリジル）−４，６−ジメルカプト−ｓ−トリアジン、等を挙げることができる。

(Here, Z is chlorine, bromine, iodine, —OH, —SH, and R ₄ is a divalent aliphatic chain having 1 to 20 carbon atoms, monocyclic or polycyclic 2 having 3 to 20 carbon atoms. Valent aliphatic ring, divalent aromatic ring, divalent heterocyclic ring, ether group having 2 to 20 carbon atoms, sulfide group having 2 to 20 carbon atoms, sulfoxide group having 2 to 20 carbon atoms, 2 to 2 carbon atoms 20 sulfone groups.)
Specific examples of the triazine compound represented by the general formula (2) include, for example, 2-methyl-4,6-dichloro-s-triazine, 2-ethyl-4,6-dichloro-s-triazine, and 2-dodecyl. -4,6-dichloro-s-triazine, 2-benzyl-4,6-dichloro-s-triazine, 2-phenyl-4,6-dichloro-s-triazine, 2-naphthyl-4,6-dichloro-s -Triazine, 2-methoxy-4,6-dichloro-s-triazine, 2-ethoxy-4,6-dichloro-s-triazine, 2-phenoxy-4,6-dichloro-s-triazine, 2-thiomethyl-4 , 6-dichloro-s-triazine, 2-thioethyl-4,6-dichloro-s-triazine, 2-thiophenyl-4,6-dichloro-s-triazine, 2-dimethylamino 4,6-dichloro-s-triazine, 2-cyclohexylamino-4,6-dichloro-s-triazine, 2-anilino-4,6-dichloro-s-triazine, 2-hydroxy-4,6-dichloro-s -Triazine, 2-cyano-4,6-dichloro-s-triazine, 2-thiocyano-4,6-dichloro-s-triazine, 2- (2-thienyl) -4,6-dichloro-s-triazine, 2 -(4-pyridyl) -4,6-dichloro-s-triazine, 2-methyl-4,6-dibromo-s-triazine, 2-ethyl-4,6-dibromo-s-triazine, 2-dodecyl-4 , 6-Dibromo-s-triazine, 2-benzyl-4,6-dibromo-s-triazine, 2-phenyl-4,6-dibromo-s-triazine, 2-naphthyl-4,6-dibro -S-triazine, 2-methoxy-4,6-dibromo-s-triazine, 2-ethoxy-4,6-dibromo-s-triazine, 2-phenoxy-4,6-dibromo-s-triazine, 2-thiomethyl -4,6-dibromo-s-triazine, 2-thioethyl-4,6-dibromo-s-triazine, 2-thiophenyl-4,6-dibromo-s-triazine, 2-dimethylamino-4,6-dibromo- s-triazine, 2-cyclohexylamino-4,6-dibromo-s-triazine, 2-anilino-4,6-dibromo-s-triazine, 2-hydroxy-4,6-dibromo-s-triazine, 2-cyano -4,6-dibromo-s-triazine, 2-thiocyano-4,6-dibromo-s-triazine, 2- (2-thienyl) -4,6-dibromo-s -Triazine, 2- (4-pyridyl) -4,6-dibromo-s-triazine, 2-methyl-4,6-diiodo-s-triazine, 2-ethyl-4,6-diiodo-s-triazine, 2 -Dodecyl-4,6-diiodo-s-triazine, 2-benzyl-4,6-diiodo-s-triazine, 2-phenyl-4,6-diiodo-s-triazine, 2-naphthyl-4,6-diiodo -S-triazine, 2-methoxy-4,6-diiodo-s-triazine, 2-ethoxy-4,6-diiodo-s-triazine, 2-phenoxy-4,6-diiodo-s-triazine, 2-thiomethyl -4,6-diiodo-s-triazine, 2-thioethyl-4,6-diiodo-s-triazine, 2-thiophenyl-4,6-diiodo-s-triazine, 2-dimethyla -4,6-diiodo-s-triazine, 2-cyclohexylamino-4,6-diiodo-s-triazine, 2-anilino-4,6-diiodo-s-triazine, 2-cyano-4,6-diiodo -S-triazine, 2-thiocyano-4,6-diiodo-s-triazine, 2- (2-thienyl) -4,6-diiodo-s-triazine, 2- (4-pyridyl) -4,6-diiodo -S-triazine, 2-methyl-4,6-dimercapto-s-triazine, 2-ethyl-4,6-dimercapto-s-triazine, 2-dodecyl-4,6-dimercapto-s-triazine, 2-benzyl -4,6-dimercapto-s-triazine, 2-phenyl-4,6-dimercapto-s-triazine, 2-naphthyl-4,6-dimercapto-s-triazine, 2 Methoxy-4,6-dimercapto-s-triazine, 2-ethoxy-4,6-dimercapto-s-triazine, 2-phenoxy-4,6-dimercapto-s-triazine, 2-thiomethyl-4,6-dimercapto- s-triazine, 2-thioethyl-4,6-dimercapto-s-triazine, 2-thiophenyl-4,6-dimercapto-s-triazine, 2-dimethylamino-4,6-dimercapto-s-triazine, 2-cyclohexyl Amino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2-mercapto-4,6-dimercapto-s-triazine, 2-cyano-4,6-dimercapto- s-triazine, 2-thiocyano-4,6-dimercapto-s-triazine, 2- (2-thieni ) -4,6-dimercapto-s-triazine, 2- (4-pyridyl) -4,6-dimercapto-s-triazine, and the like.

  Examples of the compound represented by the general formula (3) include dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,2-dichlorocyclopropane, 1,2- Dichlorocyclopentane, 1,3-dichlorocyclopentane, 1,2-dichlorocyclohexane, 1,4-dichlorocyclopentane, 1,2-dichlorocyclooctane, 1,3-dichlorocyclooctane, 1,4-dichlorocyclooctane 1,5-dichlorocyclooctane, 1,2-dichlorocyclooctahydronaphthalene, 2,6-dichlorocyclooctahydronaphthalene, 1,3-dichloroadamantane, 1,2-dichloro-1,2,5,6- Tetrahydrodicyclopentadiene, 1,5-dichloro-1,2,5,6-tetrahydride Dicyclopentadiene, 1,6-dichloro-1,2,5,6-tetrahydrodicyclopentadiene, 2,5-dichloro-1,2,5,6-tetrahydrodicyclopentadiene, 2,6-dichloro-1, 2,5,6-tetrahydrodicyclopentadiene, 2,5-dichlorothiophene, 2,6-dichloropyridine, α, α′-dichloroxylene, 4,6-dichloro-s-triazine derivative, dibromomethane, 1,2 -Bromoethane, 1,3-bromopropane, 1,4-bromobutane, 1,2-dibromocyclopropane, 1,2-dibromocyclopentane, 1,3-dibromocyclopentane, 1,2-dibromocyclohexane, 1,4 -Dibromocyclopentane, 1,2-dibromocyclooctane, 1,3-dibromocyclooctane, 1,4-di Lomocyclooctane, 1,5-dibromocyclooctane, 1,2-dibromocyclooctahydronaphthalene, 2,6-dibromocyclooctahydronaphthalene, 1,3-dibromoadamantane, 1,2-dibromo-1,2,5 , 6-tetrahydrodicyclopentadiene, 1,5-dibromo-1,2,5,6-tetrahydrodicyclopentadiene, 1,6-dibromo-1,2,5,6-tetrahydrodicyclopentadiene, 2,5- Dibromo-1,2,5,6-tetrahydrodicyclopentadiene, 2,6-dibromo-1,2,5,6-tetrahydrodicyclopentadiene, 2,5-dibromothiophene, 2,6-dibromopyridine, α, α'-dibromoxylene, 4,6-dibromo-s-triazine derivative, diiodomethane, 1,2-diio Ethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,2-diiodocyclopropane, 1,2-diiodocyclopentane, 1,3-diiodocyclopentane, 1,2-diiodocyclohexane 1,4-diiodocyclopentane, 1,2-diiodocyclooctane, 1,3-diiodocyclooctane, 1,4-diiodocyclooctane, 1,5-diiodocyclooctane, 1,2- Diiodocyclooctahydronaphthalene, 2,6-diiodocyclooctahydronaphthalene, 1,2-diiodo-1,2,5,6-tetrahydrodicyclopentadiene, 1,5-diiodo-1,2,5,6 -Tetrahydrodicyclopentadiene, 1,6-diiodo-1,2,5,6-tetrahydrodicyclopentadiene, 2,5-diiodo-1, , 5,6-tetrahydrodicyclopentadiene, 2,6-diiodo-1,2,5,6-tetrahydrodicyclopentadiene, 2,5-diiodothiophene, 2,6-diiodopyridine, α, α'- Diiodoxylene, 4,6-diiodo-s-triazine derivatives, ethylene glycol, propylene glycol, butanediol, cyclohexanedimethanol, benzenedimethanol, hydroquinone, bisphenol A, 4,4'-dihydroxyphenyl sulfoxide, 4,4 ' -Dihydroxyphenylsulfone, ethanedithiol, butanedithiol, benzenedithiol, ethylenediamine, o-diaminobenzene, m-diaminobenzene, p-diaminobenzene, 4,4'-diamino-diphenylmethane, piperazine and the like.

  The polymerization method for producing a triazine resin from the triazine compound represented by the general formula (2) and the compound represented by the general formula (3) can be performed by a general polycondensation reaction. In the polycondensation reaction, a polymerization solvent may be used. Examples of the polymerization solvent include alkanes such as pentane, octane, and nonane; cycloalkanes such as cyclohexane, cycloheptane, and cyclooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; Carboxylic acid esters such as ethyl acetate and butyl acetate; Cyclic ethers such as tetrahydrofuran; Linear dialkyl ethers such as dibutyl ether; Nitro compounds such as nitrobenzene; N-methyl-2- Polar solvents such as pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide; Halogenated alkanes such as methylene chloride, dichloroethane and chloroform; Halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Alcohols such as methanol and cyclohexanol; Water can be used, and these solvents can be used alone. Alternatively, two or more kinds of solvents may be mixed and used. In addition, when two or more kinds of solvents are used and the reaction system is separated into two phases, a phase transfer catalyst may be used to perform the polycondensation reaction more efficiently. For example, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium hydroxide, tetrapropylammonium chloride, tetrapropylammonium Bromide, tetrapropylammonium iodide, tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide , Tetrabutylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, trilaurylmethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, hexadecyltrimethylammonium Quaternary ammonium salts such as chloride, hexadecyltrimethylammonium bromide, hexadecyltripropylammonium chloride, hexadecyltributylammonium chloride, phenyltrimethylammonium chloride; tetraethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide And the like can be exemplified quaternary phosphonium salts such as bromide. The amount of use of the phase transfer catalyst is 0.01 to 50% by weight with respect to the total amount of the triazine compound represented by the general formula (2) and the compound represented by (3). It is preferable that it is the range of these.

  The polymerization temperature in the polycondensation reaction is preferably −30 ° C. to 250 ° C., and the polymerization time is preferably several minutes to 20 hours.

  The triazine resin composition of the present invention is 0.001 to 2 parts by weight, particularly preferably 0.01 to 1 part by weight of a phenol-based antioxidant and / or a phosphorus-based antioxidant with respect to 100 parts by weight of the triazine-based resin. Parts, more preferably 0.02 to 0.5 parts by weight, these antioxidants improve the thermal stability of the triazine resin composition, yellowing, reduced transparency, etc. It suppresses. Here, when the compounding quantity of a phenolic antioxidant and / or phosphorus antioxidant is less than 0.001 weight part, the thermal stability of the obtained triazine-type resin composition will become scarce. On the other hand, when the blending amount of the phenol-based antioxidant and / or the phosphorus-based antioxidant exceeds 2 parts by weight, the effect of improving the thermal stability accompanying an increase in the blending amount is small, and industrial value cannot be found. In addition, these antioxidants may be used alone or in combination, and among them, the antioxidant effect can be obtained synergistically. Therefore, a phenolic antioxidant and a phosphorus antioxidant are used in combination. In this case, the content is preferably 100 to 500 parts by weight of the phosphorus antioxidant with respect to 100 parts by weight of the phenol antioxidant, for example.

  Examples of the phenolic antioxidant used in the present invention include pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), thiodiethylene-bis (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide), diethyl ((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphate, 3, 3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri- -Cresol, ethylenebis (oxyethylene) bis (3- (5-t-butyl-4-hydroxy-m-tolyl) propionate), hexamethylene-bis (3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H ) -Trione, 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 3,9-bis (2- ( 3- (3-t-butyl-4-hydroxy 5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and the like. Among them, the triazine resin composition is colored. Pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl) Particularly preferred are -4-hydroxyphenyl) propionate and ethylenebis (oxyethylene) bis (3- (5-t-butyl-4-hydroxy-m-tolyl) propionate).

  Examples of phosphorus antioxidants used in the present invention include tris (2,4-di-t-butylphenyl) phosphite and bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl. ) Ethyl ester phosphorous acid, tetrakis (2,4-di-t-butylphenyl) (1,1-biphenyl) -4,4′-diylbisphosphonite, bis (2,4-di-t-butyl) Phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetrakis (2, 4-t-butylphenyl) (1,1-biphenyl) -4,4′-diylbisphosphonite, di-t-butyl-m-cresyl-phospho In particular, triazine-based resin compositions are difficult to be colored and are extremely excellent, so tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-di-) Particularly preferred are t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid.

  In addition, since the triazine resin composition of the present invention becomes a triazine resin composition with further improved thermal stability, the lactone stabilizer 0.001 to 2 is further added to 100 parts by weight of the triazine resin. Part by weight, more preferably 0.005 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight is preferably blended. Examples of the lactone antioxidant include 3- (3,4-dimethylphenyl) -5,7-di-t-butyl-3H-benzofuran-2-one.

  Further, the triazine-based resin composition of the present invention may contain other antioxidants such as a sulfur-based antioxidant. Examples of the sulfur-based antioxidant include dilauryl-3,3-thiodipropionate, Dimyristyl-3,3′-thiodipropionate, distearyl-3,3-thiodipropionate, laurylstearyl-3,3-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate) 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. Other antioxidants include, for example, 6- (3- (3-t-butyl-4-hydroxy-5-methyl) propoxy) -2,4,8,10-tetra-t-butyldibenz [d, f]. [1,3,2] -Dioxaphosphepine, 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-benzopyran-6 -All and the like.

  The triazine-based resin composition of the present invention can be produced by performing general mixing and kneading of the above-described triazine-based resin and a phenol-based antioxidant and / or a phosphorus-based antioxidant. Examples thereof include a mixer such as a Henschel mixer and a ribbon blender, and a melt kneader such as a single screw extruder, a twin screw extruder, a brabender, a roll, a kneader, and a Banbury mixer. Alternatively, a method may be used in which the respective components are dissolved or dispersed in a solvent and mixed.

  Furthermore, the triazine resin composition of the present invention has a hindered amine light stabilizer, an ultraviolet absorber, a light stabilizer, for the purpose of preventing thermal coloring and photodegradation due to irradiation with light such as visible light, ultraviolet light, and near infrared light. You may contain a near-infrared absorber etc. as needed. Moreover, you may contain a plasticizer as needed in the range which does not impair transparency in order to provide fluidity | liquidity and toughness. Furthermore, pigments, lubricants, antiblocking agents, antistatic agents, surfactants, polymer electrolytes, conductive complexes, inorganic fillers, dyes, oils and the like may be contained as necessary, and transparency is not impaired. Other resins may be contained only in some cases.

  The triazine-based resin composition of the present invention can be formed into a molded body by a conventionally known molding method, for example, injection molding, injection compression molding, gas assist method injection molding, extrusion molding, multilayer extrusion molding, rotational molding, hot pressing. Molding, blow molding, foam molding, etc. can be performed. In the case of a film, the triazine resin composition of the present invention may be dissolved in a solvent and formed into a film by a solution casting method. The triazine-based resin of the present invention has high heat resistance and high refractive index, and can be used as an optical material such as various plastic lenses and optical films.

  The triazine-based resin composition of the present invention has high heat resistance, stability, and high refractive index, and is useful as a raw material for various plastic lenses and optical films.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example does not restrict | limit this invention at all.

  Various physical properties shown in Synthesis Examples and Examples were measured by the following methods.

~ Measurement of weight average molecular weight ~
It calculated | required as a standard polystyrene conversion value using the gel permeation chromatography (GPC) (The Tosoh Corporation make, brand name HLC-802A).

-Measurement of refractive index (nD)-
An Abbe refractometer (trade name DR-M2 manufactured by Atago Co., Ltd.) was used, and measurement was performed by d-line.

~ Measurement of yellowness ~
Measurement was performed using a color difference meter (trade name SM color computer, manufactured by Suga Test Instruments Co., Ltd.).

~ Measurement of total light transmittance ~
It measured using the turbidimeter (Nippon Denshoku Co., Ltd. make, brand name haze meter NDH5000).

Synthesis example 1
(Synthesis of 2-anilino-4,6-dichloro-s-triazine)
A 1-liter four-necked flask equipped with a condenser, a nitrogen inlet tube, and a thermometer was charged with a rotor, 36.9 g (0.2 mol) of cyanuric chloride, and 200 ml of tetrahydrofuran (hereinafter referred to as THF) while stirring. Cooled to ° C. A solution obtained by mixing 18.8 g (0.2 mol) of aniline and 100 ml of THF was slowly added dropwise so that the reaction solution did not reach 5 ° C. or higher. After completion of the addition, stirring was continued for 1 hour. Next, 100 ml of a 1 mol / liter sodium carbonate aqueous solution was slowly added dropwise so that the reaction solution did not reach 20 ° C. or more. After completion of the addition, stirring was continued for 1 hour, and 200 ml of water was added. After liquid separation, THF in the organic layer was removed with an evaporator, and the resulting white crystals were recrystallized with toluene / hexane to obtain 36.5 g of 2-anilino-4,6-dichloro-s-triazine. The yield was 76%.

(Synthesis of triazine resin composed of 2-anilino-4,6-dichloro-s-triazine and bisphenol A)
Into a 300 ml four-necked flask equipped with a condenser, a nitrogen inlet tube, and a thermometer, a rotor, 5.7 g (25 mmol) of bisphenol A, 52 ml (52 mmol) of a 1 mol / liter aqueous sodium hydroxide solution, and 3.7 g of cetyltrimethylammonium bromide ( 10 mmol) is dissolved. A solution prepared by dissolving 6.0 g (25 mmol) of 2-anilino-4,6-dichloro-s-triazine in 60 ml of methylene chloride was added thereto, followed by stirring at room temperature overnight. The reaction solution was poured into 1 liter of methanol to precipitate the polymer. The obtained polymer was purified by reprecipitation twice with chloroform and methanol, and then dried under reduced pressure at 80 ° C. for 8 hours to obtain 8.9 g of a polymer. The yield was 90%.

In the obtained triazine-based resin, each of X, R ₁ and R ₂ represented by the general formula (1) had a structure shown in Table 1. Moreover, the weight average molecular weight was 93000 and the refractive index was 1.64.

Synthesis example 2
(Synthesis of 2-phenoxy-4,6-dichloro-s-triazine)
A liter, 36.9 g (0.2 mol) of cyanuric chloride and 200 ml of methylene chloride were placed in a 1-liter four-necked flask equipped with a cooling tube, a nitrogen introducing tube and a thermometer, and cooled to 2 ° C. with stirring. A solution prepared by dissolving 18.8 g (0.2 mol) of phenol in 100 ml of a 2 mol / liter aqueous sodium hydroxide solution was slowly added dropwise to this methylene chloride suspension so that the reaction solution would not exceed 5 ° C. After completion of the dropwise addition, stirring was continued for 3 hours, and the mixture was returned to room temperature and stirred overnight. After the suspension was filtered, methylene chloride was removed by an evaporator, and the resulting white crystals were recrystallized from hexane / chloroform to give 43.4 g of 2-phenoxy-4,6-dichloro-s-triazine. Got. The yield was 90%.

(Synthesis of triazine resin composed of 2-phenoxy-4,6-dichloro-s-triazine and o-diaminobenzene)
A rotator, 2.7 g (25 mmol) of o-diaminobenzene and 50 ml of N-methyl-2-pyrrolidone (NMP) were dissolved in a 300 ml four-necked flask equipped with a condenser, a nitrogen inlet tube and a thermometer. To this, 6 g (25 mmol) of 2-phenoxy-4,6-dichloro-s-triazine was added and reacted at 80 ° C. for 24 hours. The reaction solution was poured into 1 liter of methanol to precipitate the polymer. The obtained polymer was purified by reprecipitation twice with chloroform and methanol, and then dried under reduced pressure at 80 ° C. for 8 hours to obtain 6.6 g of a polymer. The yield was 95%.

In the obtained triazine-based resin, each of X, R ₁ and R ₂ represented by the general formula (1) had a structure shown in Table 1. Moreover, the weight average molecular weight was 85000 and the refractive index was 1.68.

Synthesis example 3
(Synthesis of 2-diphenylamino-4,6-dichloro-s-triazine)
A liter, 36.9 g (0.2 mol) of cyanuric chloride and 200 ml of methylene chloride were placed in a 1-liter four-necked flask equipped with a cooling tube, a nitrogen introducing tube and a thermometer, and cooled to 2 ° C. with stirring. A solution prepared by dissolving 33.8 g (0.2 mol) of diphenylamine and 0.2 g (0.2 mol) of triethylamine in 100 ml of methylene chloride was slowly added dropwise thereto so that the reaction solution did not reach 5 ° C. or higher. After completion of the dropwise addition, stirring was continued for 3 hours, and the mixture was returned to room temperature and stirred overnight. After the reaction solution was washed with water several times, methylene chloride was removed with an evaporator, and the obtained crystals were recrystallized with toluene / hexane to obtain 44.2 g of 2-diphenylamino-4,6-dichloro-s-triazine. . The yield was 70%.

(Synthesis of 2-diphenylamino-4,6-dimercapto-s-triazine)
In a 500 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 40 g (0.13 mol) of 2-diphenylamino-4,6-dichloro-s-triazine and 100 ml of dimethylformamide (DMF) were added and heated. To make a homogeneous solution. After cooling to room temperature, a solution obtained by dissolving 21.8 g (0.39 mol) of NaSH in 25 ml of water was slowly added dropwise so that the reaction temperature did not exceed 60 ° C., and the mixture was stirred as it was for 1 hour. When 3.5% hydrochloric acid was added to this solution until the pH reached about 4, a white precipitate was formed. The precipitate was filtered and washed thoroughly with water to obtain 29.6 g of 2-diphenylamino-4,6-dimercapto-s-triazine. The yield was 73%.

(Synthesis of triazine resin comprising 2-diphenylamino-4,6-dimercapto-s-triazine and α, α'-dibromoxylene)
A 300 ml four-necked flask equipped with a condenser, a nitrogen inlet tube, and a thermometer, rotator, 7.8 g (25 mmol) of 2-diphenylamino-4,6-dimercapto-s-triazine, 1 mol / liter sodium hydroxide 52 ml (52 mmol) of an aqueous solution and 3.7 g (10 mmol) of hexadecyltrimethylammonium bromide are added and dissolved. A solution prepared by dissolving 6.6 (25 mmol) of α, α′-dibromoxylene in 50 ml of nitrobenzene was added thereto, followed by stirring overnight at room temperature. The reaction solution was poured into 1 liter of methanol to precipitate the polymer. The obtained polymer was purified by reprecipitation twice with chloroform and methanol, and then dried under reduced pressure at 80 ° C. for 8 hours to obtain 9.3 g of a polymer. The yield was 89%.

In the obtained triazine-based resin, each of X, R ₁ and R ₂ represented by the general formula (1) had a structure shown in Table 1. Moreover, the weight average molecular weight was 102000, and the refractive index was 1.70.

Example 1
Pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) 0.05 as a phenolic antioxidant with respect to 100 parts by weight of the triazine-based resin obtained in Synthesis Example 1 Part by weight and 0.15 part by weight of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite as a phosphorus antioxidant were blended and dissolved in chloroform to prepare a resin solution. The resin solution was cast on a PET film, and chloroform was removed to obtain a triazine-based resin composition film.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, the yellowness was 2.0 and the total light transmittance was 88%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 2.2 and the total light transmittance was 88%, which was transparent. The heat stability was also excellent.

Example 2
Instead of 0.05 parts by weight of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) as a phenolic antioxidant, ethylene bis (oxyethylene) bis (3- ( 5-tert-butyl-4-hydroxy-m-tolyl) propionate)) and 0.02 parts by weight of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol A triazine-based resin composition film by the same method as in Example 1 except that 0.2 parts by weight of tris (2,4-di-t-butylphenyl) phosphite was used instead of 0.15 parts by weight of phosphite. And evaluated.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, the yellowness was 2.0 and the total light transmittance was 88%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 2.4 and the total light transmittance was 88% and the transparency. The heat stability was also excellent.

Example 3
Instead of 0.05 parts by weight of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) as a phenolic antioxidant, octadecyl-3- (3,5-di- 0.1 part by weight of t-butyl-4-hydroxyphenyl) propionate and 0.15 part by weight of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite as a phosphorus antioxidant The triazine was prepared in the same manner as in Example 1 except that 0.15 parts by weight of bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid was used instead of parts. A system resin composition film was obtained and evaluated.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, the yellowness was 2.0 and the total light transmittance was 88%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a drier adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 2.3 and the total light transmittance was 88% and transparency. The heat stability was also excellent.

Example 4
Instead of 0.05 parts by weight of pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) as a phenolic antioxidant, octadecyl-3- (3,5-di- 0.1 part by weight of t-butyl-4-hydroxyphenyl) propionate and 0.15 part by weight of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite as a phosphorus antioxidant Instead of 0.2 parts by weight, 0.2 parts by weight of tris (2,4-di-t-butylphenyl) phosphite is used, and 3- (3,4-dimethylphenyl) -5,7-di- A triazine-based resin composition film was obtained in the same manner as in Example 1 except that 0.1 parts by weight of t-butyl-3H-benzofuran-2-one was used. Evaluation was carried out.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, the yellowness was 2.0 and the total light transmittance was 88%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 2.1 and the total light transmittance was 88% and the transparency. The heat stability was also excellent.

Example 5
A triazine-based resin composition film was obtained in the same manner as in Example 1 except that the triazine-based resin obtained from Synthesis Example 2 was used instead of the triazine-based resin obtained in Synthesis Example 1, and the evaluation was performed. It was.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, the yellowness was 5.8 and the total light transmittance was 87%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a drier adjusted to 250 ° C. for 30 minutes, and then the yellowness and light transmittance were measured. As a result, the yellowness was 5.9 and the total light transmittance was 87%. The heat stability was also excellent.

Example 6
A triazine-based resin composition film was obtained in the same manner as in Example 2 except that the triazine-based resin obtained from Synthesis Example 2 was used instead of the triazine-based resin obtained in Synthesis Example 1, and the evaluation was performed. It was.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, the yellowness was 5.8 and the total light transmittance was 87%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 6.0 and the total light transmittance was 87%. The heat stability was also excellent.

Example 7
A triazine resin composition film was obtained in the same manner as in Example 3, except that the triazine resin obtained from Synthesis Example 2 was used instead of the triazine resin obtained in Synthesis Example 1, and the evaluation was performed. It was.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, the yellowness was 5.8 and the total light transmittance was 87%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a drier adjusted to 250 ° C. for 30 minutes, and then the yellowness and light transmittance were measured. As a result, the yellowness was 5.9 and the total light transmittance was 87%. The heat stability was also excellent.

Example 8
A triazine resin composition film was obtained in the same manner as in Example 4 except that the triazine resin obtained from Synthesis Example 2 was used instead of the triazine resin obtained in Synthesis Example 1, and the evaluation was performed. It was.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, the yellowness was 5.8 and the total light transmittance was 87%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a drier adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 5.8 and the total light transmittance was 87%. The heat stability was also excellent.

Example 9
A triazine-based resin composition film was obtained in the same manner as in Example 1 except that the triazine-based resin obtained from Synthesis Example 3 was used instead of the triazine-based resin obtained in Synthesis Example 1, and the evaluation was performed. It was.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, it was excellent in transparency with a yellowness of 3.4 and a total light transmittance of 86%. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 4.2 and the total light transmittance was 86%. The heat stability was also excellent.

Example 10
A triazine-based resin composition film was obtained in the same manner as in Example 2 except that the triazine-based resin obtained from Synthesis Example 3 was used instead of the triazine-based resin obtained in Synthesis Example 1, and the evaluation was performed. It was.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, it was excellent in transparency with a yellowness of 3.4 and a total light transmittance of 86%. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 4.4 and the total light transmittance was 86%. The heat stability was also excellent.

Example 11
A triazine-based resin composition film was obtained in the same manner as in Example 3 except that the triazine-based resin obtained from Synthesis Example 3 was used instead of the triazine-based resin obtained in Synthesis Example 1, and the evaluation was performed. It was.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, it was excellent in transparency with a yellowness of 3.4 and a total light transmittance of 86%. Further, the triazine-based resin composition film was heat-treated in a drier adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 4.3 and the total light transmittance was 86% and the transparency. The heat stability was also excellent.

Example 12
A triazine-based resin composition film was obtained in the same manner as in Example 4 except that the triazine-based resin obtained from Synthesis Example 3 was used instead of the triazine-based resin obtained in Synthesis Example 1, and the evaluation was performed. It was.

  When the yellowness and light transmittance of the obtained triazine-based resin composition film were measured, it was excellent in transparency with a yellowness of 3.4 and a total light transmittance of 86%. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 4.1 and the total light transmittance was 86%. The heat stability was also excellent.

Comparative Example 1
A triazine-based resin film was obtained and evaluated by the same method as in Example 1 except that only the triazine-based resin obtained in Synthesis Example 1 was used.

  When the yellowness and light transmittance of the obtained triazine-based resin film were measured, the yellowness was 2.0 and the total light transmittance was 88%, which was excellent in transparency. Further, the triazine resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 9.5, the total light transmittance was 85%, and the transparency. Decreased and the thermal stability was poor.

Comparative Example 2
A triazine-based resin film was obtained and evaluated by the same method as in Example 1 except that only the triazine-based resin obtained in Synthesis Example 2 was used.

  When the yellowness and light transmittance of the obtained triazine-based resin film were measured, the yellowness was 5.8 and the total light transmittance was 88%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 13.8, the total light transmittance was 85% and the transparency. Decreased and the thermal stability was poor.

Comparative Example 3
A triazine-based resin film was obtained and evaluated by the same method as in Example 1 except that only the triazine-based resin obtained in Synthesis Example 3 was used.

  When the yellowness and light transmittance of the obtained triazine-based resin film were measured, the yellowness was 3.4 and the total light transmittance was 86%, which was excellent in transparency. Further, the triazine-based resin composition film was heat-treated in a dryer adjusted to 250 ° C. for 30 minutes, and the yellowness and light transmittance were measured. As a result, the yellowness was 14.8, the total light transmittance was 84%, and the transparency. Decreased and the thermal stability was poor.

Claims (6)

The phenolic antioxidant and / or phosphorus antioxidant 0.001-2 weight with respect to 100 weight part of triazine resin which consists of a unit represented by the following general formula (1) and has a weight average molecular weight of 1000-1000000. A triazine-based resin composition comprising a part.

(Here, X is nitrogen, oxygen, or sulfur, R ₁ is an alkyl group having 1 to 20 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. An aromatic group, a heterocyclic compound, a cyano group, a thiocyano group, and an alkyl group having 1 to 20 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms, an aromatic group, and a heterocyclic compound May be bonded to the triazine ring via nitrogen, oxygen or sulfur, and R ₂ is a divalent aliphatic chain having 1 to 20 carbon atoms, a monocyclic or polycyclic divalent divalent chain having 3 to 20 carbon atoms. Aliphatic ring, divalent aromatic ring, divalent heterocycle, C2-C20 ether group, C2-C20 sulfide group, C2-C20 sulfoxide group, C2-C20 Represents a sulfone group.) Pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, ethylene bis It is at least one phenolic antioxidant selected from the group consisting of (oxyethylene) bis (3- (5-t-butyl-4-hydroxy-m-tolyl) propionate). The triazine-based resin composition according to 1. Tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-bis (1,1 The triazine resin composition according to claim 1 or 2, wherein the triazine resin composition is at least one phosphorus antioxidant selected from the group consisting of -dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid. object. The triazine-based resin composition according to any one of claims 1 to 3, further comprising 0.001 to 2 parts by weight of a lactone stabilizer based on 100 parts by weight of the triazine-based resin. A molded article comprising the triazine-based resin composition according to claim 1. A film comprising the triazine-based resin composition according to claim 1.