JP4063746B2 - (Meth) acrylate with novel thiourethane skeleton - Google Patents

Description

  The present invention relates to an ultraviolet curable hard coat agent component for glasses lens resin having a thiourethane bond or an epithiosulfide bond, or a (meth) acrylate that is very useful as a lens or the like.

Resin lenses are rapidly spreading as lens resins for pick-up lenses used for glasses, cameras, and optical recording / reproducing devices instead of glass lenses for reasons such as lightness, impact resistance, and colorability. Conventionally, radically polymerized diethylene glycol bis (allyl carbonate) (hereinafter abbreviated as DAC), polycarbonate (PC), polymethacrylic acid methacrylate (PMMA), and the like have been used for these purposes. These lens resins have a refractive index of n _d = 1.49 to 1.58. However, in Patent Document 1, a thiourethane bond is formed by thermal polymerization of thiol (meth) acrylate and isocyanate (meth) acrylate. The obtained resin is described, and a refractive index of about nd = 1.60 to 1.67 is obtained.

  Further, the resin obtained by forming an epithiosulfide bond by ring-opening thermal polymerization of thioepoxy (meth) acrylate described in Patent Document 2 has a refractive index of nd = 1.70 or more.

On the other hand, resin lenses have inferior surface hardness and scratch resistance compared to glass lenses, so surface hard coat treatment is indispensable, and many studies have been made on this issue as hard coat agents. An acrylate hard coating agent that is cured with ultraviolet rays is widely used. This acrylate hard coating agent can be easily cured by irradiating ultraviolet rays for several seconds to several tens of seconds in an environment of about room temperature, and the pot life of the coating solution is usually as long as 6 months or more. A. C. Various hard coat agents have been developed for PC and PMMA and are widely used in practice. However, no UV curable hard coating agent having high hardness and being in close contact with a resin lens having a thiourethane bond or an epithiosulfide bond has not been found yet, and its development is awaited.
Japanese Patent Laid-Open No. 9-110956 JP 2002-140883 A

  An object of the present invention is to provide a novel (meth) acrylate useful as an ultraviolet curable hard coat agent component having high adhesion to a resin having a thiourethane bond and an epithiosulfide bond, and having excellent surface hardness and scratch resistance. It is to provide a manufacturing method.

  In order to solve these problems, the present inventors have conducted intensive studies, and found that an ultraviolet curable hard having specific adhesion and surface hardness to a resin surface having a thiourethane bond or an epithiosulfide bond. A novel (meth) acrylate useful as a coating agent has been found.

  The (meth) acrylate having a novel thiourethane skeleton in the present invention is a (meth) acrylate that is very useful as a component of the hard coat agent, and is in close contact with a resin lens having a thiourethane bond and an epithiosulfide bond. An ultraviolet curable hard coating agent having high hardness is realized.

That is, the present invention
1. A novel (meth) acrylate represented by the general formula (1).

（１）
（式中、連結基Ｒ_１は脂肪族残基、芳香族残基、脂環族残基、複素環残基、もしくは、鎖中に酸素原子、硫黄原子、窒素原子、芳香環、脂肪族環または複素環を有する脂肪族残基を表し、Ｘ_１はＣ（＝Ｏ）Ｏ（ＣＨ_２）_１〜４基、Ｃ＝Ｏ基、Ｐｈ−Ｃ（ＣＨ_３）_２基（ここでＰｈはフェニレン基を示す）を表し、Ｘ_２はそれぞれ独立に水素原子またはメチル基を表し、ｎ_１は１〜４の整数を表す。）
２．一般式（１）におけるＸ_１がＣ（＝Ｏ）Ｏ（ＣＨ_２）_２基、連結基Ｒ１が（２）〜（６）のいずれかで表される基である１記載の新規（メタ）アクリレート。

(1)
(Wherein the linking group R ₁ is an aliphatic residue, aromatic residue, alicyclic residue, heterocyclic residue, or an oxygen atom, sulfur atom, nitrogen atom, aromatic ring, aliphatic ring in the chain) Or an aliphatic residue having a heterocyclic ring, wherein X ₁ is a C (═O) O (CH ₂ ) _1-4 group, a C═O group, a Ph—C (CH ₃ ) ₂ group (where Ph is phenylene) X ₂ represents a hydrogen atom or a methyl group, and n ₁ represents an integer of ₁ to 4).
2. _2. The novel (meta) according to 1, wherein X ₁ in the general formula (1) is a C (═O) O (CH ₂ ) ₂ group and the linking group R 1 is a group represented by any one of (2) to (6). Acrylate.

（２）

(2)

（３）

(3)

（４）

(4)

（５）

(5)

（６）
（式中、Ｘ_３は水素原子またはメチル基を表し、Ｘ_４、Ｘ_５は酸素原子または硫黄原子を表し、Ｘ_６は水素原子、メチル基またはエチル基を表し、ｎ_２は１〜５の整数、ｎ_３は0〜２の整数、ｎ_４〜ｎ_９はそれぞれ０または１の整数を表す）
３．チオールと光重合性モノイソシアネートとのチオウレタン化反応により得られる１記載の新規（メタ）アクリレート。
４．一般式（７）で表される新規（メタ）アクリレート。

(6)
(Wherein, _{X 3} represents a hydrogen atom or a methyl _group, X 4, _{X 5} represents an oxygen atom or a sulfur atom, _{X 6} represents a hydrogen atom, a methyl group or an ethyl group, _{n 2} is 1 to 5 integer, _{n 3} is an integer of 0 to _2, integer n 4 ~n ₉ are each 0 or 1)
3. 2. The novel (meth) acrylate according to 1, obtained by thiourethanation reaction between thiol and photopolymerizable monoisocyanate.
4). A novel (meth) acrylate represented by the general formula (7).

（７）
（式中、連結基Ｒ_２、Ｒ_３は脂肪族残基、芳香族残基、脂環族残基、複素環残基、もしくは、鎖中に酸素原子、硫黄原子、窒素原子、芳香環、脂肪族環または複素環を有する脂肪族残基を表し、Ｘ_６はＣ（＝Ｏ）Ｏ（ＣＨ_２）_１〜４基、Ｃ＝Ｏ基、Ｐｈ−Ｃ（ＣＨ_３）_２基（ここでＰｈはフェニレン基を示す）を表し、Ｘ_７はそれぞれ独立に水素原子またはメチル基を表し、ｎ_１０は１〜４の整数を表し、ｎ_１１は１または２の整数を表し、ｎ_１２は１〜３の整数を表す。）
５．一般式（７）におけるＸ_６がＣ（＝Ｏ）Ｏ（ＣＨ_２）_２基、連結基Ｒ２が式（２）または式（３）のいずれかで表される基であることを特徴とする４記載の新規（メタ）アクリレート。
６．分子内に２個以上のメルカプト基を有するポリチオール、光重合性モノイソシアネート、光重合性基を有さないイソシアネートのチオウレタン化反応から得られる４記載の新規（メタ）アクリレート。
７．ポリチオールの少なくとも一方のメルカプト基を残すよう光重合性モノイソシアネート（メタ）アクリレートとのモル比を調整し反応させた後、残りの未反応メルカプト基と光重合性基を有さないイソシアネートを反応させることを特徴とする４〜５のいずれかに記載の新規（メタ）アクリレートの製造方法。
８．１〜６のいずれかに記載の新規（メタ）アクリレートを含有することを特徴とするハードコート剤。
９．１〜６のいずれかに記載の新規（メタ）アクリレートよりなる光学材料。
に関する。

(7)
(Wherein the linking groups R ₂ and R ₃ are an aliphatic residue, an aromatic residue, an alicyclic residue, a heterocyclic residue, or an oxygen atom, sulfur atom, nitrogen atom, aromatic ring in the chain, Represents an aliphatic residue having an aliphatic ring or a heterocyclic ring, and X ₆ represents a C (═O) O (CH ₂ ) _1-4 group, a C═O group, a Ph—C (CH ₃ ) ₂ group (wherein Ph represents a phenylene group), X ₇ each independently represents a hydrogen atom or a methyl group, n ₁₀ represents an integer of 1 to 4, n ₁₁ represents an integer of 1 or 2, and n ₁₂ represents 1 Represents an integer of ~ 3)
5. X ₆ in the general formula (7) is a C (═O) O (CH ₂ ) ₂ group, and the linking group R 2 is a group represented by either the formula (2) or the formula (3). 4. The novel (meth) acrylate according to 4.
6). 5. A novel (meth) acrylate obtained from a thiourethanation reaction of a polythiol having two or more mercapto groups in the molecule, a photopolymerizable monoisocyanate, or an isocyanate having no photopolymerizable group.
7). After reacting by adjusting the molar ratio of the photopolymerizable monoisocyanate (meth) acrylate so as to leave at least one mercapto group of the polythiol, the remaining unreacted mercapto group and the isocyanate having no photopolymerizable group are reacted. The manufacturing method of the novel (meth) acrylate in any one of 4-5 characterized by the above-mentioned.
The hard coat agent characterized by containing the novel (meth) acrylate in any one of 8.1-6.
The optical material which consists of a novel (meth) acrylate in any one of 9.1-6.
About.

  The hard coat agent using the (meth) acrylate having a photopolymerizable group and a thiourethane bond as a component of the present invention is excellent in adhesion to a resin having a thiourethane bond and an epithiosulfide bond, and is excellent in scratch resistance. There are advantages.

The present invention will be described in detail below.
General formula (1) of the present invention

（１）
（式中、連結基Ｒ_１は脂肪族残基、芳香族残基、脂環族残基、複素環残基、もしくは、鎖中に酸素原子、硫黄原子、窒素原子、芳香環、脂肪族環または複素環を有する脂肪族残基を表し、Ｘ_１はＣ（＝Ｏ）Ｏ（ＣＨ_２）_１〜４基、Ｃ＝Ｏ基、Ｐｈ−Ｃ（ＣＨ_３）_２基（ここでＰｈはフェニレン基を示す）を表し、Ｘ_２はそれぞれ独立に水素原子またはメチル基を表し、ｎ_１は１〜４の整数を表す。）

で表される新規（メタ）アクリレートにおいて、連結基Ｒ１は脂肪族残基、芳香族残基、脂環族残基、複素環残基、もしくは、鎖中に酸素原子、硫黄原子、窒素原子、芳香環、脂肪族環または複素環を有する脂肪族残基を表し、Ｘ_１はＣ（＝Ｏ）Ｏ（ＣＨ_２）_１〜４基、Ｃ＝Ｏ基、Ｐｈ−Ｃ（ＣＨ_３）_２基（ここでＰｈはフェニレン基を示す）を表し、Ｘ_２はそれぞれ独立に水素原子またはメチル基を表し、ｎ_１は１〜４の整数を表す。

(1)
(Wherein the linking group R ₁ is an aliphatic residue, aromatic residue, alicyclic residue, heterocyclic residue, or an oxygen atom, sulfur atom, nitrogen atom, aromatic ring, aliphatic ring in the chain) Or an aliphatic residue having a heterocyclic ring, wherein X ₁ is a C (═O) O (CH ₂ ) _1-4 group, a C═O group, a Ph—C (CH ₃ ) ₂ group (where Ph is phenylene) X ₂ represents a hydrogen atom or a methyl group, and n ₁ represents an integer of ₁ to 4).

In the novel (meth) acrylate represented by the formula, the linking group R1 is an aliphatic residue, aromatic residue, alicyclic residue, heterocyclic residue, or an oxygen atom, sulfur atom, nitrogen atom in the chain, Represents an aliphatic residue having an aromatic ring, an aliphatic ring or a heterocyclic ring, and X ₁ is a C (═O) O (CH ₂ ) _1-4 group, a C═O group, a Ph—C (CH ₃ ) ₂ group. (Wherein Ph represents a phenylene group), X ₂ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of ₁ to 4.

  Moreover, as a preferable compound, the compound whose coupling group R1 in General formula (1) is group represented by either (2)-(6) is mentioned.

（２）

(2)

（３）

(3)

（４）

(4)

（５）

(5)

（６）
（式中、Ｘ_３は水素原子またはメチル基を表し、Ｘ_４、Ｘ_５は酸素原子または硫黄原子を表し、Ｘ_６は水素原子、メチル基またはエチル基を表し、ｎ_２は１〜５の整数、ｎ_３は0〜２の整数、ｎ_４〜ｎ_９はそれぞれ０または１の整数を表す）

また本発明の一般式（７）

(6)
(Wherein, _{X 3} represents a hydrogen atom or a methyl _group, X 4, _{X 5} represents an oxygen atom or a sulfur atom, _{X 6} represents a hydrogen atom, a methyl group or an ethyl group, _{n 2} is 1 to 5 integer, _{n 3} is an integer of 0 to _2, integer n 4 ~n ₉ are each 0 or 1)

The general formula (7) of the present invention

（７）
（式中、連結基Ｒ_２、Ｒ_３は脂肪族残基、芳香族残基、脂環族残基、複素環残基、もしくは、鎖中に酸素原子、硫黄原子、窒素原子、芳香環、脂肪族環または複素環を有する脂肪族残基を表し、Ｘ_６はＣ（＝Ｏ）ＯＣＨ_２ＣＨ_２基、Ｃ＝Ｏ基、Ｐｈ−Ｃ（ＣＨ_３）_２基（ここでＰｈはフェニレン基を示す）を表し、Ｘ_７はそれぞれ独立に水素原子またはメチル基を表し、ｎ_１０は１〜４の整数を表し、ｎ_１１は１または２の整数を表し、ｎ_１２は１〜３の整数を表す。）

で表される新規（メタ）アクリレートにおいて、連結基Ｒ_２、Ｒ_３は脂肪族残基、芳香族残基、脂環族残基、複素環残基、もしくは、鎖中に酸素原子、硫黄原子、窒素原子、芳香環、脂肪族環または複素環を有する脂肪族残基を表し、Ｘ_６はＣ（＝Ｏ）ＯＣＨ_２ＣＨ_２基、Ｃ＝Ｏ基、Ｐｈ−Ｃ（ＣＨ_３）_２基（ここでＰｈはフェニレン基を示す）を表し、Ｘ_７はそれぞれ独立に水素原子またはメチル基を表し、ｎ_１０は１〜４の整数を表し、ｎ_１１は１または２の整数を表し、ｎ_１２は１〜３の整数を表す。

(7)
(Wherein the linking groups R ₂ and R ₃ are an aliphatic residue, an aromatic residue, an alicyclic residue, a heterocyclic residue, or an oxygen atom, sulfur atom, nitrogen atom, aromatic ring in the chain, Represents an aliphatic residue having an aliphatic ring or a heterocyclic ring, and X ₆ is a C (═O) OCH ₂ CH ₂ group, a C═O group, a Ph—C (CH ₃ ) ₂ group (where Ph is a phenylene group) X ₇ represents each independently a hydrogen atom or a methyl group, n ₁₀ represents an integer of 1 to 4, n ₁₁ represents an integer of 1 or 2, and n ₁₂ represents an integer of 1 to 3. Represents.)

In the novel (meth) acrylate represented by the formula, the linking groups R ₂ and R ₃ are an aliphatic residue, an aromatic residue, an alicyclic residue, a heterocyclic residue, or an oxygen atom or a sulfur atom in the chain. Represents an aliphatic residue having a nitrogen atom, an aromatic ring, an aliphatic ring or a heterocyclic ring, and X ₆ represents a C (═O) OCH ₂ CH ₂ group, a C═O group, or a Ph—C (CH ₃ ) ₂ group. (Wherein Ph represents a phenylene group), X ₇ each independently represents a hydrogen atom or a methyl group, n ₁₀ represents an integer of 1 to 4, n ₁₁ represents an integer of 1 or 2, n ₁₂ represents an integer of 1 to 3.

  As a novel (meth) acrylate production method in the present invention, for example, the general formula (1) is a compound obtained by a thiourethanation reaction between a thiol and a photopolymerizable monoisocyanate, and the general formula (7) is , A compound obtained from a thiourethanation reaction of a polythiol having two or more mercapto groups in the molecule, a photopolymerizable monoisocyanate, or an isocyanate having no photopolymerizable group.

  The photopolymerizable group in the compound having a photopolymerizable group used in the present invention is not particularly limited as long as it is a group having photopolymerizability, but is preferably photoradical polymerization, photocationic polymerization, This refers to a group that reacts by photoanionic polymerization, and specifically refers to a (meth) acrylate group, vinyl group, thiol group, epoxy group, oxetane group, etc., but preferably a (meth) acrylate group from the viewpoint of the rate of photopolymerization. It is done. Details will be described below.

  Both (meth) acrylates of general formulas (1) and (7) are obtained by a thiourethanization reaction with thiol and isocyanate.

（８）
一般式（１）で表される（メタ）アクリレート得るためには、チオール（メタ）アクリレートのメルカプト基と光重合性モノイソシアネート（メタ）アクリレートのイソシアネート基のモル比が０．８〜１．２になるように調製する。０．８以下または１．２以上の場合、反応終了後も好ましくない副反応が進行しゲル化する可能性がある。
一般式（７）で表される（メタ）アクリレートを得るための好ましい手順としては、まずポリチオールの少なくとも一方のメルカプト基を残すよう光重合性モノイソシアネート（メタ）アクリレートとのモル比を調整し反応させる。

(8)
In order to obtain the (meth) acrylate represented by the general formula (1), the molar ratio of the mercapto group of the thiol (meth) acrylate and the isocyanate group of the photopolymerizable monoisocyanate (meth) acrylate is 0.8 to 1.2. Prepare to be. In the case of 0.8 or less or 1.2 or more, an undesirable side reaction may proceed and gelation may occur even after the reaction is completed.
As a preferable procedure for obtaining the (meth) acrylate represented by the general formula (7), first, the reaction is performed by adjusting the molar ratio with the photopolymerizable monoisocyanate (meth) acrylate so as to leave at least one mercapto group of the polythiol. Let

（９）
この反応が完全に完結した後、残りの未反応メルカプト基と光重合性基を有さないイソシアネートを反応させる。

(9)
After this reaction is completely completed, the remaining unreacted mercapto group is reacted with an isocyanate having no photopolymerizable group.

（１０）
一般式（１）で表されるチオ（メタ）アクリレート（メタ）アクリレートの製造に用いられるチオール（メタ）アクリレートは、特に限定されるものではないが、好ましくは脂肪族残基、芳香族残基、脂環族残基、複素環残基、もしくは、鎖中に酸素原子、硫黄原子、芳香環、脂肪族環または複素環を有する脂肪族残基を有し、かつ、メルカプト基を１つ以上有する（メタ）アクリレートである。具体的には、モノチオール（メタ）アクリレートとして、メチルメルカプタン、エチルメルカプタン、プロピルメルカプタン、ブチルメルカプタン、アミルメルカプタン、ヘキシルメルカプタン、ヘプチルメルカプタン、オクチルメルカプタン、ノニルメルカプタン、シクロペンチルメルカプタン、シクロヘキシルメルカプタン、フルフリルメルカプタン、チオフェノール、チオクレゾール、エチルチオフェノール、ベンジルメルカプタン、
ポリチオール（メタ）アクリレートとして、１，２−エタンジチオール、１，２−プロパンジチオール、１，３−プロパンジチオール、１，４−ブタンジチール、１，６−ヘキサンジチオール、１，２，３−プロパントリチオール、１，１−シクロヘキサンジチオール、１，２−シクロヘキサンジチオール、ビシクロ〔２，２，１〕ヘプタ−ｅｘｏ−ｃｉｓ−２，３−ジチオール、１，１−ビス（メルカプトメチル）シクロヘキサン、ジエチレングリコールビス（２−メルカプトアセテート）、ジエチレングリコールビス（３−メルカプトプロピオネート）、ビス（２−メルカプトエチル）エーテル、エチレングリコールビス（２−メルカプトアセテート）、エチレングリコールビス（３−メルカプトプロピオネート）、トリメチロールプロパンビス（２−メルカプトアセテート）、トリメチロールプロパンビス（３−メルカプトプロピオネート）、ペンタエリスリトールテトラキス（２−メルカプトアセテート）、ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、
１，２−ジメルカプトベンゼン、１，３−ジメルカプトベンゼン、１，４−ジメルカプトベンゼン、１，２−ビス（メルカプトメチル）ベンゼン、１，３−ビス（メルカプトメチル）ベンゼン、１，４−ビス（メルカプトメチル）ベンゼン、１，２−ビス（２−メルカプトエチル）ベンゼン、１，３−ビス（２−メルカプトエチル）ベンゼン、１，４−ビス（２−メルカプトエチル）ベンゼン、１，２−ビス（２−メルカプトエチレンオキシ）ベンゼン、１，３−ビス（２−メルカプトエチレンオキシ）ベンゼン、１，４−ビス（２−メルカプトエチレンオキシ）ベンゼン、１，２，３−トリメルカプトベンゼン、１，２，４−トリメルカプトベンゼン、１，３，５−トリメルカプトベンゼン、１，２，３−トリス（メルカプトメチル）ベンゼン、１，２，４−トリス（メルカプトメチル）ベンゼン、１，３，５−トリス（メルカプトメチル）ベンゼン、１，２，３−トリス（２−メルカプトエチル）ベンゼン、１，２，４−トリス（２−メルカプトエチル）ベンゼン、１，３，５−トリス（２−メルカプトエチル）ベンゼン、１，２，３−トリス（２−メルカプトエチレンオキシ）ベンゼン、１，２，４−トリス（２−メルカプトエチレンオキシ）ベンゼン、１，３，５−トリス（２−メルカプトエチレンオキシ）ベンゼン、
１，２，３，４−テトラメルカプトベンゼン、１，２，３，５−テトラメルカプトベンゼン、１，２，４，５−テトラメルカプトベンゼン、１，２，３，４−テトラキス（メルカプトメチル）ベンゼン、１，２，３，５−テトラキス（メルカプトメチル）ベンゼン、１，２，４，５−テトラキス（メルカプトメチル）ベンゼン、１，２，３，４−テトラキス（２−メルカプトエチル）ベンゼン、１，２，３，５−テトラキス（２−メルカプトエチル）ベンゼン、１，２，４，５−テトラキス（２−メルカプトエチル）ベンゼン、１，２，３，４−テトラキス（２−メルカプトエチレンオキシ）ベンゼン、１，２，３，５−テトラキス（２−メルカプトエチレンオキシ）ベンゼン、１，２，４，５−テトラキス（２−メルカプトエチレンオキシ）ベンゼン、２，２’−ジメルカプトビフェニル、４，４’−チオビス−ベンゼンチオール、４，４’−ジメルカプトビフェニル、４，４’−ジメルカプトビベンジル、２，５−トルエンジチオール、３，４−トルエンジチオール、１，４−ナフタレンジチオール、１，５−ナフタレンジチオール、２，６−ナフタレンジチオール、２，７−ナフタレンジチオール、２，４−ジメチルベンゼン−１，３−ジチオール、４，５−ジメチルベンゼン−１，３−ジチオール、９，１０−アントラセンジメタンチオール、
・ ２−ビス（２−メルカプトエチルチオ）ベンゼン、１，３−ビス（２−メルカプトエ
チルチオ）ベンゼン、１，４−ビス（２−メルカプトエチルチオ）ベンゼン、１，２−ビス（２−メルカプトエチルチオメチル）ベンゼン、１，３−ビス（２−メルカプトエチルチオメチル）ベンゼン、１，４−ビス（２−メルカプトエチルチオメチル）ベンゼン、１，２，３−トリス（２−メルカプトエチルチオ）ベンゼン、１，２，４−トリス（２−メルカプトエチルチオ）ベンゼン、１，３，５−トリス（２−メルカプトエチルチオ）ベンゼン、１，２，３，４−テトラキス（２−メルカプトエチルチオ）ベンゼン、１，２，３，５−テトラキス（２−メルカプトエチルチオ）ベンゼン、１，２，４，５−テトラキス（２−メルカプトエチルチオ）ベンゼン、ビス（２−メルカプトエチル）スルフィド、ビス（２−メルカプトエチルチオ）メタン、１，２−ビス（２−メルカプトエチルチオ）エタン、１，３−ビス（２−メルカプトエチルチオ）プロパン、１，２，３−トリス（２−メルカプトエチルチオ）プロパン、テトラキス（２−メルカプトエチルチオメチル）メタン、１，２−ビス（２−メルカプトエチルチオ）プロパンチオール、２，５−ジメルカプト−１，４−ジチアン、ビス（２−メルカプトエチル）ジスルフィド、３，４−チオフェンジチオール、１，２−ビス（２−メルカプトエチル）チオ−３−メルカプトプロパン、ビス−（２−メルカプトエチルチオ−３−メルカプトプロパン）スルフィド等が挙げられる。

(10)
The thiol (meth) acrylate used for the production of the thio (meth) acrylate (meth) acrylate represented by the general formula (1) is not particularly limited, but is preferably an aliphatic residue or an aromatic residue. , An alicyclic residue, a heterocyclic residue, or an aliphatic residue having an oxygen atom, a sulfur atom, an aromatic ring, an aliphatic ring or a heterocyclic ring in the chain, and one or more mercapto groups It has (meth) acrylate. Specifically, as methylthiol (meth) acrylate, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, furfuryl mercaptan, furfuryl mercaptan Thiophenol, thiocresol, ethylthiophenol, benzyl mercaptan,
1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol as polythiol (meth) acrylate 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, bicyclo [2,2,1] hepta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, diethylene glycol bis (2 -Mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpro Nbisu (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate),
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (2-mercaptoethyl) benzene, 1,3-bis (2-mercaptoethyl) benzene, 1,4-bis (2-mercaptoethyl) benzene, 1,2- Bis (2-mercaptoethyleneoxy) benzene, 1,3-bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1, 2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) ben 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (2-mercaptoethyl) benzene, 1,2,4-tris (2-mercaptoethyl) benzene, 1,3,5-tris (2-mercaptoethyl) benzene, 1,2,3-tris (2-mercaptoethyleneoxy) benzene, 1,2,4-tris (2-mercapto Ethyleneoxy) benzene, 1,3,5-tris (2-mercaptoethyleneoxy) benzene,
1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyl) benzene, 2,3,5-tetrakis (2-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2-mercaptoethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (2-mercaptoethyleneoxy) Benzene, 2,2′-dimercaptobiphenyl, 4,4′-thiobis-benzenethiol, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4 -Toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethyl Benzene-1,3-dithiol, 9,10-anthracene dimethanethiol,
2-bis (2-mercaptoethylthio) benzene, 1,3-bis (2-mercaptoethylthio) benzene, 1,4-bis (2-mercaptoethylthio) benzene, 1,2-bis (2-mercapto) Ethylthiomethyl) benzene, 1,3-bis (2-mercaptoethylthiomethyl) benzene, 1,4-bis (2-mercaptoethylthiomethyl) benzene, 1,2,3-tris (2-mercaptoethylthio) Benzene, 1,2,4-tris (2-mercaptoethylthio) benzene, 1,3,5-tris (2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis (2-mercaptoethylthio) Benzene, 1,2,3,5-tetrakis (2-mercaptoethylthio) benzene, 1,2,4,5-tetrakis (2-mercaptoethylthio) Benzene, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethylthio) methane, 1,2-bis (2-mercaptoethylthio) ethane, 1,3-bis (2-mercaptoethylthio) propane, 1 , 2,3-tris (2-mercaptoethylthio) propane, tetrakis (2-mercaptoethylthiomethyl) methane, 1,2-bis (2-mercaptoethylthio) propanethiol, 2,5-dimercapto-1,4 -Dithiane, bis (2-mercaptoethyl) disulfide, 3,4-thiophenedithiol, 1,2-bis (2-mercaptoethyl) thio-3-mercaptopropane, bis- (2-mercaptoethylthio-3-mercaptopropane) ) Sulfide and the like.

  The photopolymerizable monoisocyanate (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having both the above-described photopolymerizable group and isocyanate group in the structure. Specifically, Examples include 2-methacryloyloxyethyl isocyanate, 2-methacryloyloxymethyl isocyanate, 2-methacryloyloxypropyl isocyanate, 2-methacryloyloxybutyl isocyanate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-methylacryloyl isocyanate. 2-Methacryloyloxyethyl isocyanate is preferably used because of its ease of treatment.

  The isocyanate having no photopolymerizable group used for synthesizing the (meth) acrylate of the general formula (7) is not particularly limited, but specifically, the monoisocyanate includes ethyl isocyanate and cyclohexyl. Examples include isocyanate, phenyl isocyanate, tolyl isocyanate, benzyl isocyanate, propyl isocyanate, hexyl isocyanate, octyl isocyanate and methoxypropyl isocyanate. Examples of the diisocyanate include propane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (cyclohexyl isocyanate), Trimethylhexamethylene diisocyanate, tolylene diisocyanate, 4,4-diphenylmeta Diisocyanate, xylene diisocyanate, hydrogenated xylylene diisocyanate, norbornane Socia sulfonates, and the like methyl norbornane Socia sulfonates.

  The catalyst used for the above thiourethanation reaction is not particularly limited, but is preferably organic tin (meth) acrylate such as dibutyltin dilaurate, dibutyltin acetate, dibutyltin dichloride, tin octylate, zinc octylate, naphthenic acid. Organic zinc (meth) acrylates such as zinc, tertiary amines such as triethylenediamine and triethylamine, (meth) acrylates having an amidine skeleton such as 1,8-diazabicyclo [5,4,0] undecene-7 are used, and thiol Or it adds in 0.0001-10 weight part with respect to 100 weight part of isocyanate.

  In the above reaction, a temperature range of −50 ° C. to 100 ° C. is usually applied. Below -50 ° C, the progress of the reaction is extremely slow. Above 100 ° C, by-products increase and the yield decreases, and the degree of coloring increases, which is not preferable. Dilute with a solvent if necessary. Solvents used can be used except alcohols, carboxylic acids, amines and the like that react with isocyanates. From the viewpoint of reaction rate and solubility, N, N-dimethylformamide (DMF), N, N— Polar solvents such as dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), chlorinated solvents such as chloroform, and aromatic solvents such as toluene and xylene are preferably used. A dehydrated solvent is preferably used to prevent the reaction between residual water and isocyanate.

  In the reaction between thiol and photopolymerizable isocyanate, it is preferable to add a polymerization inhibitor in order to prevent an undesirable side reaction (so-called ene-thiol reaction) between the thiol and the photopolymerizable group. As the polymerization inhibitor to be used, quinones such as hydroquinone and benzoquinone, phenols such as p-methoxyphenol, N-nitrosophenylhydroxylamine salts and the like are used.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to an Example.

Using a 200 ml four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 50.0 g of dehydrated N, N-dimethylformamide (DMF) as a solvent, 2-mercaptoethyl sulfide ( After charging 10.0 g (0.075 mol) of Tokyo Kasei Kogyo Co., Ltd., 20 g (0.13 mol) of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK: product name Karenz MOI) was used as a catalyst. 04 g, a pre-prepared N-nitrosophenylhydroxylamine aluminum salt 0.004 g as a polymerization inhibitor was added dropwise over 30 minutes from the dropping funnel. Thereafter, the temperature was raised from room temperature to 40 ° C. and the reaction was carried out as it was. The progress of the reaction is performed by infrared absorption spectrum (IR) analysis, and the point at which sharp absorption due to an isocyanate group near 2260 cm −1 and absorption due to an SH group near 2580 cm −1 are not completely recognized. The end point of the reaction was taken. This reaction solution is poured into a large amount of water to precipitate the product, then dissolved again in chloroform, washed with water, the oil layer is dehydrated with anhydrous sodium sulfate, and the solvent is distilled off by a vacuum method to obtain a transparent viscous product. Was recovered. (Recovery rate: 98.3%)
This product was subjected to IR analysis and NMR analysis, and it was confirmed that the (meth) acrylate compound (11) was obtained.
IR: 1680 cm-1: thiourethane group, 3300-3400 cm-1: -NH-
¹ H-nuclear magnetic resonance spectrum (CDCl 3 solvent, TMS standard) σ (ppm)
8.00 (s, 2H, —N H —), 5.00 to 7.00 (m, 4H, C═C H ₂ cis / trans), 4.00 to 4.50 (t, 4H, NH— _{CH 2 C H 2), 3.00~4.00} (m, 4H, NH-C H 2 CH 2 or _{m, 8H,, SC H 2} C H 2 S), 1.9~2.0 (m , 6H, CC H ₃ = CH ₂ )

（１１）

(11)

A 200 ml four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was used, and 50.0 g of dehydrated DMF as a solvent, 1,2-bis (2-mercaptoethyl) thio-3-mercapto After charging 10.0 g (0.038 mol) of propane, 17.6 g (0.114 mol) of 2-methacryloyloxyethyl isocyanate was used as a catalyst, 0.04 g of dibutyltin dilaurate, and N-nitrosophenylhydroxylamine aluminum as a polymerization inhibitor. What was previously prepared in 0.004 g of salt was dropped from the dropping funnel over 30 minutes. Thereafter, the temperature was raised from room temperature to 40 ° C., and the reaction was carried out as it was. The progress of the reaction is performed by infrared absorption spectrum (IR) analysis, and the point at which sharp absorption due to an isocyanate group near 2260 cm −1 and absorption due to an SH group near 2580 cm −1 are not completely recognized. The end point of the reaction was taken.
Thereafter, the product (compound (12)) was recovered by the same method as in Example 1.
IR: 1680 cm-1: thiourethane group, 3300-3400 cm-1: -NH-
¹ H-nuclear magnetic resonance spectrum (CDCl 3 solvent, TMS standard) σ (ppm)
_{8.00 (s, 3H, -N H} -), 5.00~7.00 (m, 6H, C = C H 2 cis / trans), 4.00~4.50 (t, 6H, NH- _{CH 2 C H 2), 2.50~4.00} (m, 6H, NH-C H 2 CH 2 or _{m, 8H,, SC H 2} C H 2 S or m, 5H,,
_{SC H 2 C H (S)} C H 2 S), 1.9~2.0 (m, 9H, C (C H 3) = CH 2)

（１２）

(12)

A 200 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used, 50.0 g of dehydrated DMF as a solvent, 10.0 g of 1,4-dimercaptobenzene (manufactured by Lancaster) ( 0.070 mol), 21.8 g (0.14 mol) of 2-methacryloyloxyethyl isocyanate as a catalyst, 0.04 g of dibutyltin dilaurate, and 0.004 g of N-nitrosophenylhydroxylamine aluminum salt as a polymerization inhibitor What was prepared in advance was dropped over 30 minutes from the dropping funnel. Thereafter, the temperature was raised from room temperature to 40 ° C., and the reaction was carried out as it was. The progress of the reaction is performed by infrared absorption spectrum (IR) analysis, and the point at which sharp absorption due to an isocyanate group near 2260 cm −1 and absorption due to an SH group near 2580 cm −1 are not completely recognized. The end point of the reaction was taken. Thereafter, the product (compound (13)) was recovered by the same method as in Example 1.
IR: 1680 cm-1: thiourethane group, 3300-3400 cm-1: -NH-
¹ H-nuclear magnetic resonance spectrum (CDCl 3 solvent, TMS standard) σ (ppm)
8.00 (s, 2H, —N H —), 6.8 to 7.2 (m, 4H, C ₆ H ₄ ), 5.00 to 7.00 (m, 4H, C═C H ₂ cis) _{/trans),4.00~4.50(t,4H,NH-CH 2 C H 2), 3.00~4.00} (m, 4H, NH-C H 2 CH 2), 1.9~ 2.0 (m, 6H, C (C H ₃ ) = CH ₂ )

（１３）

(13)

A 200 ml four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was used, and 50.0 g of dehydrated DMF and 5.0 g (0.053 mol) of 1,2-ethanedithiol were charged as solvents. Thereafter, 16.4 g (0.106 mol) of 2-methacryloyloxyethyl isocyanate was added dropwise with 0.04 g of dibutyltin dilaurate as a catalyst and 0.004 g of N-nitrosophenylhydroxylamine aluminum salt as a polymerization inhibitor. It was dripped over 30 minutes from the funnel. Thereafter, the temperature was raised from room temperature to 40 ° C., and the reaction was carried out as it was. The progress of the reaction is performed by infrared absorption spectrum (IR) analysis, and the point at which sharp absorption due to an isocyanate group near 2260 cm −1 and absorption due to an SH group near 2580 cm −1 are not completely recognized. The end point of the reaction was taken. Thereafter, the product (compound (14)) was recovered by the same method as in Example 1.
IR: 1680 cm-1: thiourethane group, 3300-3400 cm-1: -NH-
¹ H-nuclear magnetic resonance spectrum (CDCl 3 solvent, TMS standard) σ (ppm)
8.00 (s, 2H, —N H —), 5.00 to 7.00 (m, 4H, C═C H ₂ cis / trans), 4.00 to 4.50 (t, 4H, NH— _{CH 2 C H 2), 3.00~4.00} (m, 4H, NH-C H 2 CH 2 or _{m, 4H,, SC H 2} C H 2 S), 1.9~2.0 (m , 6H, C (C H ₃ ) ═CH ₂ )

（１４）

(14)

A 200 ml four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was used, 50.0 g of dehydrated DMF as a solvent, bis- (2-mercaptoethylthio-3-mercaptopropane) sulfide 10 After charging 0.0 g (0.027 mol), 16.9 g (0.108 mol) of 2-methacryloyloxyethyl isocyanate was used as a catalyst, 0.04 g of dibutyltin dilaurate, and N-nitrosophenylhydroxylamine aluminum salt 0 as a polymerization inhibitor. What was previously charged to 0.004 g was dropped over 30 minutes from the dropping funnel. Thereafter, the temperature was raised from room temperature to 40 ° C., and the reaction was carried out as it was. The progress of the reaction is performed by infrared absorption spectrum (IR) analysis, and the point at which sharp absorption due to an isocyanate group near 2260 cm −1 and absorption due to an SH group near 2580 cm −1 are not completely recognized. The end point of the reaction was taken. Thereafter, the product (compound (15)) was recovered by the same method as in Example 1.
IR: 1680 cm-1: thiourethane group, 3300-3400 cm-1: -NH-
¹ H-nuclear magnetic resonance spectrum (CDCl 3 solvent, TMS standard) σ (ppm)
8.00 (s, 4H, —N H —), 5.00 to 7.00 (m, 8H, C═C H ₂ cis / trans), 4.00 to 4.50 (t, 4H, NH— _{CH 2 C H 2), 2.50~4.00} (m, 8H, NH-C H 2 CH 2 or _{m, 8H,, SC H 2} C H 2 S or _{m,, 10H, SC H 2} C H C H ₂ S), 1.9 to 2.0 (m, 12H, CC H ₃ = CH ₂ )

（１５）

(15)

A 200 ml four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was used, and 50.0 g of dehydrated DMF and 10.0 g (0.075 mol) of 2-mercaptoethyl sulfide were charged as solvents. Thereafter, 10 g (0.075 mol) of 2-methacryloyloxyethyl isocyanate was prepared by adding 0.04 g of dibutyltin dilaurate as a catalyst and 0.004 g of N-nitrosophenylhydroxylamine aluminum salt as a polymerization inhibitor from a dropping funnel. It was added dropwise over a period of minutes. Thereafter, the temperature was raised from room temperature to 40 ° C., and the reaction was carried out as it was. Three hours later, infrared absorption spectrum (IR) analysis was performed, and it was confirmed that no absorption due to an isocyanate group in the vicinity of 2260 cm −1 was observed. One was a photopolymerizable group and the other was a compound having an SH group (16 ) Was synthesized.

（１６）
つづいて、この反応液にイソホロンジイソシアネート（東京化成工業製）７．２ｇ（０．０３２４）を３０分かけて滴下し、４０℃のまま反応を行った。１０時間後さらに６０℃まで昇温しイソシアネート基とＳＨ基に起因する吸収を確認しながら反応を継続した。それぞれの吸収が完全に認められなくなった時点を反応の終点とした。その後、実施例１と同様の方法により、生成物（化合物（１７））を回収した。
ＩＲ：１６８０ｃｍ−１：チオウレタン基、３３００〜３４００ｃｍ−１：−ＮＨ−
^１Ｈ−核磁気共鳴スペクトル（ＣＤＣｌ３溶媒、ＴＭＳ基準）σ（ｐｐｍ）
８．００（ｓ、４Ｈ、−ＮＨ−）、５．００〜７．００（ｍ、４Ｈ、Ｃ＝ＣＨ _２ ｃｉｓ／ｔｒａｎｓ）、４．００〜４．５０（ｔ、４Ｈ、ＮＨ―ＣＨ _２ ＣＨ _２）、２．５０〜４．００（ｍ、４Ｈ、ＮＨ―ＣＨ _２ ＣＨ_２、またはｍ、１６Ｈ、ＳＣＨ _２ ＣＨ _２ Ｓ、またはｍ、２Ｈ、ＮＨＣＨ _２−シクロ環、またはｍ、１Ｈ、ＮＨ−ＣＨ）、１．９〜２．０（ｗ、６Ｈ、ＣＣＨ _３ ＝ＣＨ_２、またはｓ、６Ｈ、シクロ環−Ｈ _２、またはｍ、９Ｈ、シクロ環−ＣＨ _３）

(16)
Subsequently, 7.2 g (0.0324) of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the reaction solution over 30 minutes, and the reaction was performed at 40 ° C. After 10 hours, the temperature was further raised to 60 ° C., and the reaction was continued while confirming absorption due to isocyanate groups and SH groups. The end point of the reaction was defined as the time point at which each absorption was not completely observed. Thereafter, the product (compound (17)) was recovered by the same method as in Example 1.
IR: 1680 cm-1: thiourethane group, 3300-3400 cm-1: -NH-
¹ H-nuclear magnetic resonance spectrum (CDCl 3 solvent, TMS standard) σ (ppm)
8.00 (s, 4H, —N H —), 5.00 to 7.00 (m, 4H, C═C H ₂ cis / trans), 4.00 to 4.50 (t, 4H, NH— _{CH 2 C H 2), 2.50~4.00} (m, 4H, NHC H 2 CH 2 or _{m,, 16H, SC H 2} C H 2 S or _{m, 2H,, NHC H 2} - cyclo Ring, or m, 1H, NH—C H ), 1.9-2.0 (w, 6H, CC H ₃ ═CH ₂ , or s, 6H, cyclo- H ₂ , or m, 9H, cyclo-ring -C H ₃₎

（１７）

(17)

First, compound (16) was synthesized in the same manner as in Example 6.
Then, 6.7 g (0.0324) of norbornane disociate (a mixture of 2,5-NBDI and 2,6-NBDI manufactured by NBDI Mitsui Chemicals) was dropped into this reaction solution over 30 minutes, and the temperature was kept at 40 ° C. Reaction was performed. After 10 hours, the temperature was further raised to 60 ° C., and the reaction was continued while confirming absorption due to isocyanate groups and SH groups. The end point of the reaction was defined as the time point at which each absorption was not completely observed. Thereafter, the product (compound (18)) was recovered by the same method as in Example 1.
IR: 1680 cm-1: thiourethane group, 3300-3400 cm-1: -NH-
¹ H-nuclear magnetic resonance spectrum (CDCl 3 solvent, TMS standard) σ (ppm)
8.00 (s, 4H, —N H —), 5.00 to 7.00 (m, 4H, C═C H ₂ cis / trans), 4.00 to 4.50 (t, 4H, NH— _{CH 2 C H 2), 2.50~4.00} (m, 4H, NHC H 2 CH 2 or _{m,, 16H, SC H 2} C H 2 S or _{m, 4H,, NHC H 2} - norbornane ), 1.9~2.5 (w, 6H, CC H 3 = CH 2 or s, 4H, norbornane, - H, or m, 6H, norbornane, - _H 2)

（１８）

(18)

A 20% methyl cellosolve dispersion was prepared by solvent substitution of a 30% silicon dioxide methanol dispersion (product name: Optolake, manufactured by Nissan Chemical Co., Ltd.) having a particle size of 10 to 20 nm by a concentration method. 8.0 g of this dispersion (solid content: 1.6 g) (342 parts by weight as a dispersion), 1.17 g (50 parts by weight) of the compound of Example 1, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer (Kyoeisha) 1. After mixing 1.17 (50 parts by weight) of chemical trade name UA-306I), 2.0 g (85.5 parts by weight) of DMF and 3.0 g (128 parts by weight) of methyl cellosolve were added. Further, 0.14 g (4.3 parts by weight) of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TMDPO) as a photoinitiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd. Product Darocur 1173) 0.1 g (4.3 parts by weight) was added, and the mixture was sufficiently stirred to prepare a coating composition. This coating composition was spin coated and UV cured on a 2 mm thick plate obtained by thermally curing a monomer for thiourethane lenses (product name: MR-7, manufactured by Mitsui Chemicals) to form a 2 μm coating layer. Obtained.
The surface was rubbed with No. 000 steel wool, but no scratches were seen. Moreover, although cross-cut adhesion tape peeling (100 eyes) was performed along JIS-K5400, peeling was not seen (100/100).

In Example 8, a coating composition was prepared in the same manner except that the compound of Example 1 was changed to the methacrylate of Example 6. This coating composition was spin-coated and UV-cured on a 5 mm thick plate obtained by thermally curing an epithiosulfide lens monomer (product name: MR-174 manufactured by Mitsui Chemicals), and a coating layer of 2 μm. Got.
The surface was rubbed with No. 000 steel wool, but no scratches were seen. Moreover, although cross-cut adhesion tape peeling (100 eyes) was performed along JIS-K5400, peeling was not seen (100/100).

[Comparative Example 1]
In Example 8, a coating composition was prepared in the same manner except that the compound of Example 1 was changed to pentaerythritol triacrylate. This coating composition was spin-coated and UV-cured on a 5 mm thick plate obtained by thermally curing a monomer for thiourethane lenses (product name: MR-7, manufactured by Mitsui Chemicals) to form a 2 μm coating layer. Obtained.
The surface was rubbed with No. 000 steel wool, but no scratches were seen. On the other hand, when cross-cut adhesion tape peeling (100 eyes) was performed according to JIS-K5400, the coat layer was completely peeled off (0/100).

  The novel (meth) acrylates of the present invention are used in the field of coating agents and optical materials, more specifically, high-refractive-index spectacle lens hard coats, plasma displays, liquid crystal displays, EL displays and other antireflection applications, and high-density recording light. Useful for applications such as surface coating agents for the purpose of improving the design of optical materials such as high refractive index films for reading and writing media, optical filters, and plastic materials, metal materials, ceramic materials, and glass materials. . Especially as a hard coating agent, it has excellent adhesion and hardness even on resin surfaces with thiourethane bonds and epithiosulfide bonds. It can be widely applied to hard coating agents.

Claims (6)

A novel (meth) acrylate represented by the general formula (1).

(1)
[Wherein, the linking group R ₁ represents _one of the following (3), (5), (6), X ₁ represents a C (═O) O (CH ₂ ) ₂ group, and X ₂ represents Independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of ₁ to 4. ]

(3)

(5)

(6)
(In the formulas (3), (5) and (6) above, X ₄ and X ₅ represent an oxygen atom or a sulfur atom, X ₆ represents a hydrogen atom, a methyl group or an ethyl group, and n ₃ represents 1 to 2 integer, _{n 4} and _{n 7} are each an integer of 0 or 1, _{n 8} and _{n 9} represents an integer of 1)   The novel (meth) acrylate according to claim 1, which is obtained by thiourethanation reaction between thiol and photopolymerizable monoisocyanate. A novel (meth) acrylate represented by the general formula (7).

(7)
[Wherein, the linking group R ₂ represents — (CH ₂ ) ₂ —S— (CH ₂ ) ₂ —, R ₃ represents an alicyclic residue, and X ₆ represents C (═O) O (CH ₂ ) ₂ groups, X ₇ each independently represents a hydrogen atom or a methyl group, and n ₁₂ represents an integer of 1 to 3. ]   The novel (meth) acrylate of Claim 3 obtained from the thiourethanation reaction of the polythiol which has two or more mercapto groups in a molecule | numerator, the photopolymerizable monoisocyanate, and the isocyanate which does not have a photopolymerizable group.   After reacting by adjusting the molar ratio of the photopolymerizable monoisocyanate (meth) acrylate so as to leave at least one mercapto group of the polythiol, the remaining unreacted mercapto group and the isocyanate having no photopolymerizable group are reacted. The manufacturing method of the novel (meth) acrylate of Claim 3 characterized by the above-mentioned.   A hard coat agent comprising the novel (meth) acrylate according to claim 1.