JP4313137B2 - Hard coating agent - Google Patents

Description

  The present invention relates to a photopolymerizable compound having a thiourethane skeleton and an ultraviolet curable hard coat agent which can be used for a resin containing inorganic ultrafine particles and having a thiourethane bond and an epithiosulfide bond.

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. However, since these lens resins have a refractive index of n _d = 1.49 to 1.58, in order to obtain optical characteristics equivalent to those of a glass lens, the center thickness, edge thickness, and curvature of the lens are increased. Resin having higher refractive index has been demanded because of the necessity and overall thickness.
As a countermeasure against such a problem, Patent Document 1 describes a resin obtained by thermally polymerizing a thiol compound and an isocyanate compound to form a thiourethane bond, and has a refractive index of about nd = 1.60 to 1.67. Has been obtained.
In addition, a resin obtained by forming an epithiosulfide bond by ring-opening thermal polymerization of a thioepoxy compound described in Patent Document 2 has a refractive index of nd = 1.70 or more.
Along with these countermeasures, resin lenses have inferior surface hardness and scratch resistance compared to glass lenses, and therefore, hard coating treatment on the surface is indispensable, and many studies have been made on this problem.
As the hard coat treatment, there is a so-called sol-gel method described in Patent Document 3 in which a silane coupling agent is used and a film is formed by thermosetting. This sol-gel method requires a high temperature of 100 ° C. or more and a curing time of 2 hours or more to form a film, and the storage stability (pot life) of the coating solution is usually about one month. However, since the hard coat film has very high scratch resistance and very high adhesion to a resin lens, D.I. A. It is widely used for lens resins having C, PC, PMMA, thiourethane bonds and epithiosulfide bonds.

On the other hand, a coating film having high scratch resistance can also be formed by a method (ultraviolet curable) of polyfunctional acrylate. Compared with the sol-gel method, the method using a polyfunctional acrylate 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 liquid is usually 6 months or longer. D. 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 Japanese Patent Publication No.57-2735

  An object of the present invention is to provide an ultraviolet curable hard coat agent having high adhesion to a resin having a thiourethane bond and an epithiosulfide bond, high surface hardness, high scratch resistance, and excellent liquid storage stability. There is.

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 coating agent, more specifically, a compound having a photopolymerizable group and a thiourethane bond, an ultrafine particle having an average particle diameter of 1 to 200 nm, and a hard coating agent containing a polyfunctional urethane (meth) acrylate as a component is a thiourethane. It has been found that the adhesiveness to a resin having a bond or an epithiosulfide bond is high, and the surface hardness and scratch resistance are excellent.
That is, the present invention
1. A hard coat agent comprising the following components (A) and (B) in the composition.
Component (A): Compound represented by general formula (1) Component (B): Inorganic ultrafine particles

（式中、連結基Ｒ_１は下記式（３）、（５）、（６）のいずれかを表し、Ｘ_１はＣ（＝Ｏ）Ｏ（ＣＨ _２ ） _２ 基を表し、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。）

(In the formula, the linking group R ₁ represents any of the following formulas (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 n1 represents an integer of ₁ to 4.)

（上記式（３）、（５）、（６）中、Ｘ_４、Ｘ_５は酸素原子または硫黄原子を表し、Ｘ _６ｂ は水素原子、メチル基またはエチル基を表し、ｎ_３は１〜２の整数、ｎ_４およびｎ_７はそれぞれ０または１の整数を表し、ｎ_８およびｎ_９は１の整数を表す）
２．下記成分（Ａ）および（Ｂ）を組成物中に含有することを特徴とするハードコート剤。
成分（Ａ）：一般式（７ａ）で表される化合物
成分（Ｂ）：無機超微粒子

(The above formula (3), (5), (6) in, _X 4, _{X 5} represents an oxygen atom or a sulfur atom, _{X 6b} represents a hydrogen atom, a methyl group or an ethyl group, _{n 3} is 1-2 And n ₄ and n ₇ each represent an integer of 0 or 1, and n ₈ and n ₉ represent an integer of 1)
2. A hard coat agent comprising the following components (A) and (B) in the composition.
Component (A): Compound represented by formula (7a) Component (B): Inorganic ultrafine particles

(Wherein linking group R ₂ Is-(CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Represents R ₃ Represents an alicyclic residue and X _6a Is C (= O) O (CH ₂ ) ₂ Represents the group X ₇ Each independently represents a hydrogen atom or a methyl group, and n ₁₂ Represents an integer of 1 to 3. )
3. A hard coat agent comprising the following components (A) and (B) in the composition.
Component (A): Compound represented by the general formula (7)
Component (B): Inorganic ultrafine particles

(Wherein linking group R ₂ Represents a group represented by the formula (3), and X ₆ Is C (= O) O (CH ₂ ) _1-4 Group, C═O group, Ph—C (CH ₃ ) ₂ Represents a group (where Ph represents a phenylene group), X ₇ Each independently represents a hydrogen atom or a methyl group, and n ₁₀ Represents an integer of 1 to 4 and n ₁₁ Represents an integer of 1 or 2, n ₁₂ Represents an integer of 1 to 3. )

4). The hard according to any one of 1 to 3, wherein the inorganic ultrafine particles are ultrafine particles having an average particle diameter of 1 to 200 nm containing one or more selected from metal chalcogenides or metal fluorides Coating agent.
5). 5. In addition to components (A) and (B), the component (C) contains a urethane (meth) acrylate having two or more (meth) acryloyl groups. Hard coat agent.
6). A cured film with a film thickness of 2 μm applied to the surface of a resin having a thiourethane bond or an epithiosulfide bond and cured with ultraviolet rays,
[1] Cross-cut tape method peel test (JIS-K5400) has an evaluation score of 6 or more
[2] Pencil scratch test value (JIS-K5400) is 3H or more
The ultraviolet curable hard coat agent according to any one of 1 to 5, which is
The lens containing the hard-coat agent in any one of 7.1-6.

  The hard coat agent of the present invention relates to an ultraviolet curable hard coat agent that can be used for a resin having a thiourethane bond or an epithiosulfide bond. There is an advantage that it is excellent.

  The present invention will be described in detail below.

  The hard coat agent of the present invention is a composition comprising (a) a compound having a photopolymerizable group and a thiourethane bond and (b) inorganic ultrafine particles, and is adhered to a resin having a thiourethane bond and an epithiosulfide bond. Coating layer having excellent properties and scratch resistance can be easily formed. Further, by containing a urethane-based (meth) acrylate having two or more polymerizable photopolymerizable groups as the component (C), a coat layer having higher scratch resistance can be obtained.

  In the present invention, the component (A) is not particularly limited as long as it is a compound having a photopolymerizable group and a thiourethane bond, but a compound represented by the general formula (1) is preferably used.

（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。）

(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 general formula (1), the linking group R1 is an aliphatic residue, aromatic residue, alicyclic residue, 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 ₁ 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 ₂ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of ₁ to 4.

  More preferably, a compound in which the linking group R1 in the general formula (1) is a group represented by any one of (2) to (6) is exemplified.

（２）

(2)

（３）

(3)

（４）

(4)

（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 _６ｂ 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、成分（Ａ）として、以下の一般式（７）で表される化合物も好適に用いられる。

(Wherein, _{X 3} represents a hydrogen atom or a methyl _group, X 4, _{X 5} represents an oxygen atom or a sulfur atom, _{X 6b} is a hydrogen atom, a methyl group or an ethyl group, _{n 2} is 1 to 5 An integer, n ₃ represents an integer of 0 to 2, and n _{4 to} n ₉ each represents an integer of 0 or 1)
Moreover, the compound represented by the following General formula (7) is also used suitably as a component (A).

（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。）

(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 general formula (7), 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 in the chain. Represents an aliphatic residue having 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, 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.

  The photopolymerizable group in the compound having a photopolymerizable group and a thiourethane bond used in the present invention is not particularly limited as long as it is a group having photopolymerizability, but is preferably photoradical polymerization. , Refers to a group that reacts by photocationic polymerization, photoanionic polymerization, specifically (meth) acryloyl group, vinyl group, isopropenyl group, styryl group, α-methylstyryl group, thiol group, ethynyl group, epoxy group, An oxetane group and the like can be mentioned, but a (meth) acryloyl group, a vinyl group, a styryl group, and an α-methylstyryl group are preferable from the viewpoint of a photopolymerization rate, and a (meth) acryloyl group is most preferable. . The compound preferably used as the compound having a photopolymerizable group and a thiourethane bond is the aforementioned general formula (1), more specifically, a (meth) acryloyl group and a linking group R are represented by the above formulas (2) to ( It is a group represented by any one of 6) or a compound represented by the general formula (7).

  The general formula (1) in the present invention is a compound obtained by, for example, a thiourethanation reaction between a thiol and a photopolymerizable monoisocyanate, and the general formula (7) is, for example, two or more mercapto in the molecule. It is a compound obtained from a thiourethanation reaction of a polythiol having a group, a photopolymerizable monoisocyanate, and an isocyanate having no photopolymerizable group. This will be described below.

  The compounds of the general formulas (1) and (7) can be obtained by a thiourethanation reaction with thiol and isocyanate.

（８）
一般式（１）で表される化合物を得るためには、チオール化合物のメルカプト基と光重合性モノイソシアネート化合物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など希望する性能が発現しない可能性がある。

(8)
In order to obtain the compound represented by the general formula (1), the compound is prepared so that the molar ratio of the mercapto group of the thiol compound to the isocyanate group of the photopolymerizable monoisocyanate compound is 0.8 to 1.2. In the case of 0.8 or less or 1.2 or more, there is a possibility that the desired performance such as gelation occurs due to an undesirable side reaction even after the reaction is completed.

  As a preferred procedure for obtaining the compound represented by the general formula (7), first, the molar ratio with the photopolymerizable monoisocyanate compound is adjusted so as to leave at least one mercapto group of the polythiol and reacted.

（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）アクリレート化合物の製造に用いられるチオール化合物は、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つ以上有する化合物である。具体的には、モノチオール化合物として、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、
ポリチオール化合物として、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 compound used for the production of the thio (meth) acrylate compound represented by the general formula (1) is not particularly limited, but preferably an aliphatic residue, 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. Specifically, as a monothiol compound, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, furfuryl mercaptan, phenol Thiocresol, ethylthiophenol, benzyl mercaptan,
As polythiol compounds, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 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), trimethylolpropane bis (2 − Le 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 compound is not particularly limited as long as it is a compound having both the above-mentioned photopolymerizable group and isocyanate group in the structure, and specifically, 2-methacryloyloxyethyl isocyanate. , 2-methacryloyloxymethyl isocyanate, 2-methacryloyloxypropyl isocyanate, 2-methacryloyloxybutyl isocyanate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-methylacryloyl isocyanate. -Methacryloyloxyethyl isocyanate is preferably used.

  The isocyanate having no photopolymerizable group used when synthesizing the compound of the general formula (7) is not particularly limited. Specifically, the monoisocyanate includes ethyl isocyanate, cyclohexyl isocyanate, Examples thereof include 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, methylenebis (cyclohexyl isocyanate), trimethylhexa Methylene diisocyanate, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate Over DOO, xylene diisocyanate, hydrogenated xylylene diisocyanate, norbornane Socia sulfonates, and the like methyl norbornane Socia sulfonates.

  The catalyst used in the above thiourethanation reaction is not particularly limited, but is preferably an organic tin compound such as dibutyltin dilaurate or dibutyltin dichloride, a tertiary amine such as triethylenediamine or triethylamine, and 1,8-diazabicyclo [ A compound having an amidine skeleton such as 5,4,0] undecene-7 is used and added in an amount of 0.0001 to 10 parts by weight with respect to 100 parts by weight of thiol or isocyanate.

  The above reaction is usually carried out in a temperature range of −50 ° C. to 100 ° C., and diluted with a solvent as necessary. Solvents used can be used except alcohols, carboxylic acids, amines and the like that react with isocyanates. From the viewpoint of reaction rate, N, N-dimethylformamide (DMF), N, N-dimethylacetamide ( A polar solvent such as DMAc), dimethyl sulfoxide (DMSO), or N-methyl-2-pyrrolidone (NMP), a chlorinated solvent such as chloroform, or an aromatic solvent such as toluene or xylene is preferably used.

  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.

  In the present invention, (b) the inorganic ultrafine particles are preferably metal chalcogenides such as metal oxides and metal sulfides, or metal fluorides. Specifically, titanium oxide, zirconium oxide, indium oxide, zinc oxide, Selenium oxide, antimony oxide, tin oxide, lanthanum oxide, neodymium oxide, zinc sulfide, antimony sulfide, aluminum oxide, neodymium fluoride, lanthanum fluoride, silicon dioxide, magnesium fluoride, sodium fluoride, calcium fluoride, lithium fluoride The refractive index can be adjusted by appropriately adjusting the type and blending amount of the ultrafine particles according to the use, purpose, and refractive index of the resin to be coated.

  Specifically, in order to increase the refractive index, inorganic ultrafine particles having a high refractive index are blended. In particular, in order to realize a refractive index of 1.7 or more, a refractive index of 1.8 or more is preferable at a wavelength of 546 nm. Titanium oxide, zirconium oxide, indium oxide, zinc oxide, selenium oxide, antimony oxide, oxidation Ultrafine particles containing one or more components of tin, lanthanum oxide, neodymium oxide, zinc sulfide and antimony sulfide, preferably containing one or more components of titanium oxide, zirconium oxide, zinc oxide, antimony oxide, tin oxide and zinc oxide Inorganic ultrafine particles.

On the other hand, when it is desired to adjust the refractive index of the composition to decrease, inorganic ultrafine particles having a refractive index of 1.6 or lower, specifically silicon dioxide, fluorinated, which is lower than the refractive index of thio (meth) acrylate. Inorganic ultrafine particles such as neodymium, lanthanum fluoride, magnesium fluoride, sodium fluoride, and calcium fluoride may be blended.
In addition, when aiming to ensure the transparency of the resin to be coated, when the thickness of the coating layer is 2 μm, the average transmittance at a wavelength of 400 to 600 nm is preferably 80% or more, more preferably 90% or more. preferable.

  The inorganic ultrafine particles containing two or more components are specifically a structure in which one inorganic ultrafine particle is coated with one or more other inorganic substances (core-shell structure), and a crystal structure is formed by two or more components. Things.

The particle diameter of the inorganic ultrafine particles is 1 to 200 nm, preferably 1 to 50 nm, more preferably 1 to 20 nm, and still more preferably 1 to 10 nm. When the particle diameter is larger than 200 nm, it becomes difficult to obtain a transparent coating layer due to scattering by the particles, and when it is smaller than 1 nm, the refractive index is difficult to improve.
In addition, the production method of inorganic ultrafine particles is roughly divided into a pulverization method and a synthesis method. Furthermore, as a synthesis method, there are a gas phase method such as an evaporation condensation method and a gas phase reaction method, a liquid phase method such as a colloid method, a uniform precipitation method, a hydrothermal synthesis method, and a microemulsion method.

The method for producing the inorganic ultrafine particles used in the present invention is not particularly limited, but those produced by a synthesis method are preferred from the viewpoints of particle size, composition uniformity, impurities, and the like.
Each inorganic ultrafine particle is preferably dispersed and stabilized in a solvent, water, etc., and then a coating agent is preferably prepared, and γ-glycidoxypropyltrimethoxysilane or (meth) is used to such an extent that there is no significant decrease in refractive index. Add silane coupling agents such as acryloyloxypropyltrimethoxysilane and mercaptopropyltrimethoxysilane, organic acids such as carboxylic acid, polymers such as polyvinylpyrrolidone and polyvinyl alcohol, or chemically bond them to the surface of fine particles (surface Those modified and stabilized by a method such as (modification) are preferably used.

The content of the inorganic ultrafine particles is 1 to 400 parts by weight, preferably 5 to 300 parts by weight, more preferably 100 parts by weight based on the total weight of the compounds having a photopolymerizable group and a thiourethane bond contained in the composition. 10 to 200 parts by weight.
If the content of ultrafine particles is small, an improvement in the refractive index cannot be expected, but if the content is large, defects in the coating film or adhesion to the substrate may be impaired. In addition, not only one kind of inorganic ultrafine particles but also two or more kinds may be blended. Moreover, you may mix | blend 2 or more types of the particle | grains from which the shape and particle diameter differ by the same component.
(A) A compound obtained from a thiourethanation reaction between a thiol and a photopolymerizable monoisocyanate, or obtained from a thiourethanation reaction of a polythiol having two or more mercapto groups in the molecule, a photopolymerizable monoisocyanate, or a saturated isocyanate. By adding a (meth) acrylate compound having (c) a urethane bond and having two or more photopolymerizable groups to the composition containing the compound and (b) inorganic ultrafine particles, surface hardness and scratch resistance Is further improved.
(C) The (meth) acrylate compound having a urethane bond is obtained by the reaction of the diisocyanate and hydroxy (meth) acrylate exemplified above. Specifically, as hydroxy (meth) acrylate, 2-hydroxyethyl (meth) Urethanes obtained by a combination of acrylate, 2-hydroxypropyl acrylate, glycidol methacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Examples include (meth) acrylate oligomers.

  Of these, in order to increase the hardness after curing, the number of (meth) acryloyl groups is 2 or more, preferably 3 or more, more preferably 4 or more, and diisocyanate and hydroxy (meth) acrylate are added to pentaerythritol tris. Those using (meth) acrylate are particularly preferred.

  In addition, you may use these (meth) acrylate compounds which have a urethane bond 1 type or in mixture of 2 or more types according to the physical property of hardened | cured material.

Each component in the composition, (a) a compound obtained by thiourethanation reaction between thiol and photopolymerizable monoisocyanate, (b) inorganic ultrafine particles, (c) urethane system having two or more photopolymerizable groups ( A desirable ratio of the meth) acrylate compound is in the following range from the viewpoint of surface hardness, adhesion, and the like.
(A): (c) = 1 wt%: 99 wt% to 99 wt%: 1 wt%, preferably 5 wt%: 95 wt% to 95 wt%: 5 wt%, more preferably 10 wt%: 90% to 90% by weight: 10% by weight
(B) / ((a) + (b) + (c)) = 1 to 90% by weight, preferably 5 to 80% by weight, more preferably 10 to 70% by weight It is.
When the amount of the inorganic ultrafine particles is small in the composition, it is difficult to adjust the refractive index. On the other hand, when the amount is large, problems such as the film becoming brittle and insufficient adhesion occur.

  Furthermore, in order to adjust the physical properties of the cured product, an acrylic oligomer / monomer other than thioacrylate having two or more (meth) acryloyloxy groups in one molecule may be blended.

  Specifically, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1.6-hexanediol di (meth) acrylate, 1.9-nonanediol di (Meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, 1,1,3,3,5,5-hexa ((meth) acrylic) Carboxymethyl) cyclotri phosphonium Zen, 1,1,3,3,5,5 hexa (meth) acryloxyethyl oxy) cyclotri phosphonium Zen, and the like.

A (meth) acrylic monomer having one (meth) acryloyl group per molecule may also be blended for the purpose of adjusting the viscosity. Specifically, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, methoxy-polyethylene Glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydride Kishi 3- phenoxypropyl (meth) acrylate, (meth) acrylic acid, meth) glycidyl acrylate,
2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethylphthalic acid, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meta ) Acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl methacrylate, benzyl (meth) acrylate, (meth) acryloylmorpholine, perfluorooctyl (meth) acrylate, trifluoroethyl ( And (meth) acrylate.

  A reactive monomer having several vinyl groups or thiol groups may also be added for the purpose of viscosity adjustment or curability control.

  Specifically, N-vinylpyrrolidone, N-vinylcarbazole, vinyl acetate, trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate) ), Pentaerythritol (3-mercaptopropionate), and the like.

  Moreover, in order to accelerate | stimulate hardening by an ultraviolet-ray or a heat | fever, you may mix | blend light or a thermal-polymerization initiator.

  As the photopolymerization initiator, commercially available products may be used, but specific examples include benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (product of Ciba Specialty Chemicals Co., Ltd.) Cure 651), 1-hydroxy-cyclohexyl-phenyl-ketone (product of Ciba Specialty Chemicals Co., Ltd. Irgacure 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals ( Co., Ltd. Product Darocur 1173 Lamberti Co. product Esacure KL200), Oligo (2-hydroxy-2-methyl-1-phenyl-propan-1-one) (Lamberti Co. product Esacure KIP150), (2-hydroxyethyl) -phenyl) -2- Hydroxy-2-methyl-1-propan-1-one) (Ciba Specialty Chemicals Co., Ltd. Irgacure 2959), 2-methyl-1 (4- (methylthio) phenyl) -2-morpholin propan-1-one (Ciba Specialty Chemicals Co., Ltd. product Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Specialty Chemicals Co., Ltd. product Irgacure 369), Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (product of Ciba Specialty Chemicals Co., Ltd. Irgacure 819), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine Oxide (Ciba Specialties) Culls Co., Ltd. product CGI403), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (= Lucirin TPO Ciba Specialty Chemicals Co., Ltd. product Darocur TPO, manufactured by TMDPO BASF), thioxanthone or its derivatives, etc. 1 Use a seed or a mixture of two or more.

  Further, a tertiary amine such as triethanolamine, ethyl-4-dimethylaminobenzoate, isopentylmethylaminobenzoate or the like may be added for the purpose of photosensitization.

  As the thermal polymerization initiator, a peroxide such as benzoyl peroxide (= BPO) or an azo compound such as azobisisobutylnitrile (= AIBN) is mainly used. The amount to be blended is usually about 0.1 to 10 parts by weight with respect to 100 parts by weight of the composition ((meth) acrylate + inorganic ultrafine particles).

  In general, when a small amount of a photo (thermal) polymerization initiator is added, good curability may not be obtained, and if it is too large, performance proportional to the amount cannot be obtained and the decomposition product is cured. It may adversely affect the physical properties of the material.

  When adding a solvent, water or a polar organic solvent, that is, a lower alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, methyl cellosolve, ethyl cellosolve , Butyl cellosolve, ethylene glycol, tetrahydrofuran, dioxane, low-polarity solvent toluene and the like, the viscosity of the coating liquid is adjusted by the method of coating on the substrate, preferably 0.1 cp-10000 cp, more preferably It is 0.5 cp to 500 cp, more preferably 1 cp to 100 cp.

  In addition to these, various additives such as an ultraviolet absorber, an antioxidant, and a silicon surfactant can be blended in the hard coat agent composition depending on the purpose.

Examples of evaluation methods for adhesion and surface hardness of the hard coat film include a cross-cut tape method peel test (JIS-K5400) and a pencil scratch test value (JIS-K5400). A cured film with a thickness of 2 μm
[1] The score of the cross-cut tape method peel test (JIS-K5400) is preferably 6 or more, more preferably 8 or more.
[2] The pencil scratch test value (JIS-K5400) is preferably 3H or more, more preferably 4H or more.

  The storage stability of the composition is preferably 1 month or more when stored at room temperature, 6 months or more when stored at refrigerator (4 ° C.), more preferably 6 months or more when stored at room temperature, and 1 year or more when stored at refrigerator (4 ° C.). .

[Coating method, curing method, molding method]
In the case of coating on a substrate, methods such as dip, spin coating and spraying can be employed.
As an ultraviolet light source necessary for photopolymerization, various low-pressure, high-pressure, and ultrahigh-pressure mercury lamps, chemical lamps, metal halide lamps, ultraviolet lasers, and the like can be used. The time for photopolymerization is preferably 1 second to 10 minutes. When the time is shorter than 1 second, the photocuring is not sufficiently performed, and when the time is longer than 10 minutes, the coat film and the base material may be deteriorated, and coloring or cracking may occur. For curing, after coating the substrate, the solvent is dried as necessary. The drying temperature and time are determined by the boiling point of the solvent used.
The temperature condition necessary for the thermal polymerization is generally 50 ° C. or higher, preferably 80 ° C. or higher, but is determined by the boiling point of the solvent used, the heat resistant temperature of the substrate, and the type of thermal polymerization initiator.

[Use of composition of the present invention]
The composition of the present invention can be used in a wide range because it is excellent in scratch resistance and adhesion when applied and cured on a substrate such as a resin and has very high transparency. In particular, it can also be used for resins having a thiourethane bond or an epithiosulfide bond, for which there has been no preferred material in terms of adhesion. In addition, since the refractive index of the composition of the present invention can be adjusted, it can be used as a hard coat film for spectacles, camera lenses, pickup lenses for optical recording / reproducing equipment, film lenses, liquid crystal displays, EL displays, Used to protect the surface of so-called printed materials such as anti-reflective layers for CRT displays, color separation color filters used in liquid crystal elements, guide plates, signs, posters, etc., and reduce the reflection of light from the surface of printed materials. It can also be used as a printed surface protective film, as well as an antireflection layer for window materials, light covers, and helmet shields.
Furthermore, as a surface protection material for optical recording media, a high refractive index film for reading and writing of high-density recording optical media, from the viewpoint of aesthetics, surface decorations such as resin materials, metal materials, ceramic materials, glass materials, artificial marble, etc. It can also be used as an adhesive for bonding optical materials such as lenses and optical waveguides.
Hereinafter, the present invention will be described in more detail based on production examples and examples, but the present invention is not limited to the production examples and examples.

1. Synthesis synthesis example 1 of compound having photopolymerizable group and thiourethane bond
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%)
The product was subjected to IR analysis, NMR analysis and elemental analysis to confirm that compound (11) was obtained.
IR: 1680 cm-1: thiourethane group, 3300-3400 cm-1: -NH-

（１１）

(11)

Synthesis example 2
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.

（１２）

(12)

Synthesis example 3
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, and 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.

（１３）

(13)

Synthesis example 4
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.

（１４）

(14)

Synthesis example 5
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.

（１５）

(15)

Synthesis Example 6
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。

(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 carried out 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.

（１７）

(17)

Synthesis example 7
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.

（１８）

(18)

2. Preparation 1 of inorganic ultrafine particle dispersion
Preparation of silicon dioxide (silica) ultrafine particle dispersion Made by Nissan Chemical Co., Ltd. 30 wt% methanol dispersion of silicon dioxide ultrafine particles (trade name Snowtex) is converted to methyl cellosolve by a concentration method to give a solid content of 20% A methyl cellosolve dispersion was obtained.

Production Example 2
Synthesis of zirconium oxide-titanium oxide composite oxide ultrafine particles and preparation of dispersion 7.5 ml of titanium oxychloride / hydrochloric acid aqueous solution (Fluka reagent hydrochloric acid: 38 to 42%, Ti: about 15%) (corresponding to Ti: 0.036 mol) Was dissolved in 1000 ml of ion-exchanged water. Stir at a temperature of 70 ° C. After 5 hours, a bluish titanium oxide colloidal aqueous solution was obtained.
After adjusting the pH of the colloidal aqueous solution to near 5 by ion dialysis, the solvent is converted to methyl cellosolve by a concentration method, and 1.0 g of acrylic acid is further added as a dispersing agent, followed by thorough stirring. A methyl cellosolve dispersion of titanium oxide was obtained. A part of the obtained sol solution was dropped onto a mesh to prepare an electron microscope observation sample, which was observed and confirmed to be a titanium oxide crystal having an average particle diameter of 5 nm.
To the colloidal solution, 6.4 g (Zr: equivalent to 0.020 mol) of zirconium oxychloride octahydrate was added, the temperature of the reaction solution was set to 100 ° C., and the mixture was stirred for 5 hours. As a result, a bluish white slurry-like sol solution was obtained. After adjusting the pH of the aqueous colloidal solution to about 5 by ion dialysis, the solvent is converted to methyl cellosolve by a concentration method, 1.0 g of acrylic acid is added as a dispersant, and the mixture is sufficiently stirred. A methyl cellosolve dispersion of zirconium oxide-coated titanium oxide ultrafine particles was obtained. (Composite oxide 1)

Production Example 3
Preparation of antimony oxide ultrafine particle dispersion manufactured by Nissan Chemical Co., Ltd. 30% by weight methanol dispersion of antimony oxide (trade name: AMT-130S, antimony oxide particle diameter: 10 to 20 nm) was converted to methyl cellosolve by a concentration method to obtain a solid content. A 20% by weight methyl cellosolve dispersion was obtained.

Production Example 4
Preparation of tin oxide-titanium dioxide-zirconium oxide-antimony oxide composite oxide ultrafine particle dispersion manufactured by Nissan Chemical Co., Ltd. Tin oxide-titanium dioxide-zirconium oxide-antimony oxide composite oxide 30 wt% methanol dispersion (trade name HIT-301M1, particle size 5 15 nm) of methanol was converted to methyl cellosolve by a concentration method to obtain a methyl cellosolve dispersion having a solid content of 20%. (Composite oxide 2)

Production Example 5
Preparation of Tin Oxide-Zirconium Oxide-Antimony Oxide Composite Oxide Ultrafine Particle Dispersion Methanol dispersion (trade name HX-300M1, particle size 5-15 nm) of 30% by weight tin oxide-zirconium oxide-antimony oxide composite oxide manufactured by Nissan Chemical Co., Ltd. Was converted to methyl cellosolve by a concentration method to obtain a methyl cellosolve dispersion having a solid content of 20%. (Composite oxide 3)
3. Preparation and evaluation of hard coat containing composition of the present invention

Production Example 6
Preparation of resin having thiourethane bond (1)
36.4 g of m-xylylene diisocyanate represented by the formula (19), 33.6 g of 1,2-bis (2-mercaptoethyl) thio-3-mercaptopropane represented by the formula (20) and dibutyltin dichloride 0.01 g and 0.07 g of ZelecUN (STEPAN) as an internal mold release agent were added and stirred, and degassed for 1 hour under reduced pressure. After filtration through a 1 μm Teflon (registered trademark) filter, it was poured into a molding mold comprising a glass mold and a gasket. While the mold was gradually heated from 40 ° C. to 120 ° C., polymerization was performed in 20 hours. After the polymerization was completed, the resin was gradually cooled and the resin was taken out from the mold. The obtained resin was annealed at 120 ° C. for 3 hours to obtain a resin plate (thickness 5 mm).

（１９）

（２０）

(19)

(20)

Production Example 7
Preparation of resin having thiourethane bond (2)
37.6 g of m-xylylene diisocyanate, 33.6 g of an isomer mixture represented by the formulas (21) to (23), 0.01 g of dibutyltin dichloride, and 0.07 g of ZelecUN (STEPAN) as an internal release agent. In addition, the mixture was stirred and degassed for 1 hour under reduced pressure. After filtration through a 1 μm Teflon (registered trademark) filter, it was poured into a molding mold comprising a glass mold and a gasket. While the mold was gradually heated from 40 ° C. to 120 ° C., polymerization was performed in 20 hours. After the polymerization was completed, the resin was gradually cooled and the resin was taken out from the mold. The obtained resin was annealed at 120 ° C. for 3 hours to obtain a resin plate (thickness 5 mm).

  (18) / (19) / (20) = 80/10/10 (molar ratio)

（２１）

(21)

（２２）

(22)

（２３）

(23)

Production Example 8
Preparation of resin having thiourethane bond (3)
37.6 g of m-xylylene diisocyanate, 27.6 g of bis-2-mercaptoethyl ether represented by the formula (24), 0.01 g of dibutyltin dichloride, and 0.07 g of ZelecUN (STEPAN) as an internal release agent In addition, the mixture was stirred and degassed for 1 hour under reduced pressure. After filtration through a 1 μm Teflon (registered trademark) filter, it was poured into a molding mold comprising a glass mold and a gasket. While the mold was gradually heated from 40 ° C. to 120 ° C., polymerization was performed in 20 hours. After the polymerization was completed, the resin was gradually cooled and the resin was taken out from the mold. The obtained resin was annealed at 120 ° C. for 3 hours to obtain a resin plate (thickness 5 mm).

（２４）

(24)

Production Example 9
Preparation of resin having epithiosulfide bond (1)
70.0 g of bis (2,3-epithiopropyl) disulfide represented by the formula (25), 0.014 g of N, N-dimethylcyclohexylamine and 0.07 g of N, N-dicyclohexylmethylamine were added and stirred. For 1 hour under reduced pressure. After filtration through a 3 μm Teflon (registered trademark) filter, it was poured into a molding mold comprising a glass mold and a gasket over 4 hours. After this mold was kept at 30 ° C. for 10 hours, the temperature was gradually raised from 30 ° C. to 80 ° C., and polymerization was carried out in 20 hours. After the polymerization was completed, the resin was gradually cooled and the resin was taken out from the mold. The obtained resin was annealed at 120 ° C. for 3 hours to obtain a resin plate (thickness 5 mm).

（２５）

(25)

Production Example 10
Preparation of resin having epithiosulfide bond (2)
To 70.0 g of bis (β-epithiopropyl) sulfide represented by the formula (26), 0.35 g of tributylamine was added and stirred, followed by degassing under reduced pressure for 1 hour. After filtration with a 3 μm Teflon (registered trademark) filter. The mold was poured over 4 hours. After this mold was kept at 30 ° C. for 10 hours, the temperature was gradually raised from 30 ° C. to 120 ° C., and polymerization was carried out in 20 hours. After the polymerization was completed, the resin was gradually cooled and the resin was taken out from the mold. The obtained resin was annealed at 120 ° C. for 3 hours to obtain a resin plate (thickness 5 mm).

（２６）
なお、作製例１０〜１４で作製した樹脂板は、後述の評価を実施する前、表面に付着した内部離形剤を除去するために、１重量％ＮａＯＨ水中に２０分間浸漬した後、充分水洗いを行い、室温で乾燥させた。

(26)
The resin plates produced in Production Examples 10 to 14 were sufficiently washed with water after being immersed in 1% by weight NaOH water for 20 minutes in order to remove the internal release agent adhering to the surface before carrying out the evaluation described later. And dried at room temperature.

8.0 g (solid content 1.6 g) (342 parts by weight of the dispersion) of silicon dioxide 20% methyl cellosolve dispersion having a particle diameter of 10 to 20 nm of Preparation Example 1 and 1.17 g (50 of the compound of Synthesis Example 1) Part by weight), 1.17 (50 parts by weight) g of pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer (Kyoeisha Chemical Co., Ltd., trade name UA-306I), and then mixed with 2.0 g (85.5 parts by weight) of DMF, methyl cellosolve 3 0.0 g (128 parts by weight) was 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) 0.1g (4.3 weight part) was added, it stirred well, the coating composition was prepared, and it evaluated by the below-mentioned method.

[Examples 2 to 9]
Except having changed into the composition shown in Table 1, each composition of Examples 2-7 was prepared by operation similar to Example 1, and evaluated by the method of the below-mentioned.

[Comparative Example 1]
Synthesis Example 1 in Example 1 The same composition was prepared except that the compound was changed to trimethylolpropane trimethacrylate, and evaluation was performed by the method described later.

[Comparative Example 2]
The same composition was prepared except that the compound of Synthesis Example 1 in Example 1 was changed to diethylene glycol dimethacrylate, and evaluated by the method described later.

[Comparative Example 3]
A similar composition was prepared except that a 20% silicon dioxide methyl cellosolve dispersion having a particle diameter of 10 to 20 nm in Production Example 1 of Example 1 was not added, and evaluation was performed by the method described below.

Evaluation of the hard coat agent was performed as follows.
Each of Examples 1 to 9 and Comparative Examples 1 to 3 was applied to the resin plates of Preparation Examples 6 to 10 by spin coating, dried in a hot air dryer at 40 ° C. for 1 minute, and then 160 W / cm type. A high pressure mercury lamp (light intensity at a wavelength of 365 nm: 170 mW / cm 2) was irradiated for 20 seconds to form a hard coat film having a thickness of 2 μm. The thickness was confirmed with a stylus type surface shape measuring instrument (DekTakIII ULVAC).
[1] Adhesion test Samples with a film prepared using each of Examples 1 to 9 and Comparative Examples 1 to 3 on the resin plates prepared in Preparation Examples 6 to 10 were subjected to JIS K5400 cross-cut tape method. Using a cutter guide (JIS K5400 standard) on the surface of the substrate with a coating film, cuts are made at intervals of 1 mm with a cutter knife to form 100 squares of 1 mm2. A cellophane adhesive tape (JIS Z1522 standard) was strongly pressed onto it, and after pulling it abruptly, the squares on which the coating film remained were counted.

Evaluation score 10: No peeling 8: Peeling of the defective part is within 5% of the whole 6: Peeling of the defective part is within 5-15% of the whole 4: 4: Peeling of the defective part is within 15-35% of the whole 2: Defect The peeling of the part is within 35 to 65% of the whole. 0: The peeling of the defective part is 65% or more of the whole. The results are shown in Table 1.
[2] About the sample with a film produced using each of Examples 1 to 9 and Comparative Examples 1 to 3 on the resin plate obtained in Pencil Hardness Test Production Example 6, according to JIS-K5400 The test was conducted by the scratching method.
Evaluation was performed by a method of evaluating by scratching the coating film, and the pencil hardness was examined in the range of 9H to 6B.
The results are listed in Table 1.
[3] Scratch resistance test No. 0000 steel wool (Nippon Steel Co., Ltd.) for samples with membranes prepared on Examples 1-9 and Comparative Examples 1-3 on the resin plate obtained in Preparation Example 6. A load of 200 g was applied with Wool Co., Ltd., and the surface was rubbed for 10 reciprocations, and the degree of scratching was visually judged at the next stage.
A: There is no scratch at all in the range of 1 cm × 3 cm.
B: 1 to 10 scratches are in the above range.
C: There are 10 to 30 scratches within the above range.
D: Countless scratches within the above range.
The results are listed in Table 1.
[4] Peeling test after 200 hours of irradiation with a solar simulator for samples with films produced on the resin plate obtained in Light Resistance Test Production Example 6 using Examples 1 to 9 and Comparative Examples 1 to 3 The state change before and after irradiation was investigated.
◯: No change in adhesion Δ: Slightly reduced adhesion ×: Significantly reduced adhesion results are shown in Table 1.
[5] Appearance and transmittance The sample with a film prepared using each of Examples 1 to 9 and Comparative Examples 1 to 3 on the resin plate obtained in Preparation Example 6 was visually observed to determine the transmittance. The transmittance between 400 nm and 600 nm was measured with a transmittance meter (Shimadzu UV2200).
○: 90% or more of transmittance between 400 nm and 600 nm Δ: Transmittance of 80 to 90% between 400 nm and 600 nm
X: The transmittance between 400 nm and 600 nm was 80% or less.
[6] Storage stability of hard coat agent Each of the samples prepared in Examples 1 to 9 and Comparative Examples 1 to 3 was placed in a brown sample bottle and completely sealed, and then at room temperature for 1 month, at 4 ° C for 6 months, in a dark room. The change was investigated by storing it still.
○: No gelation of the liquid and no change in viscosity Δ: No gelation of the liquid, but the viscosity changed.
X: The liquid gelled.
As a result, in all cases, at room temperature for 1 month, at 4 ° C., there was no gelation of the liquid and no change in viscosity was observed.

  The resin composition of the present invention comprises a thio (meth) acrylate compound and inorganic ultrafine particles as essential components, and can form a coat layer that can be arbitrarily adjusted in refractive index and is excellent in scratch resistance by curing with ultraviolet rays. Therefore, it can be used for coating agents and optical materials, and more specifically, for high-refractive-index eyeglass lens hard coating, plasma display, liquid crystal display, EL display, etc. It is useful for applications such as refractive index films, optical members such as optical filters, and surface coating agents for the purpose of improving the design properties of plastic materials, metal materials, ceramic materials, glass materials and the like.

  In particular, as a hard coating agent, it is excellent in adhesion and hardness even on a resin surface having a thiourethane bond or an epithiosulfide bond, such as a spectacle lens, a lens for a camera, a pickup lens for an optical recording / reproducing device, etc. It can be widely applied to hard coating agents.

Claims (7)

A hard coat agent comprising the following components (A) and (B) in the composition.
Component (A): Compound represented by general formula (1) Component (B): Inorganic ultrafine particles

(In the formula, the linking group R ₁ represents any of the following formulas (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 n1 represents an integer of ₁ to 4.)

(The above formula (3), (5), (6) in, _X 4, _{X 5} represents an oxygen atom or a sulfur atom, _{X 6b} represents a hydrogen atom, a methyl group or an ethyl group, _{n 3} is 1-2 integer, and display the integer _{n 4} and _{n 7} are each 0 or 1, _{n 8} and _{n 9} are to Table 1 integer) A hard coat agent comprising the following components (A) and (B) in the composition.
Component (A): Compound represented by the general formula (7a)
Component (B): Inorganic ultrafine particles

(Wherein linking group R ₂ Is-(CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Represents R ₃ Represents an alicyclic residue and X _6a Is C (= O) O (CH ₂ ) ₂ Represents the group X ₇ Each independently represents a hydrogen atom or a methyl group, and n ₁₂ Represents an integer of 1 to 3. ) A hard coat agent comprising the following components (A) and (B) in the composition.
Component (A): Compound represented by the general formula (7)
Component (B): Inorganic ultrafine particles

(Wherein linking group R ₂ Represents a group represented by the formula (3), and X ₆ Is C (= O) O (CH ₂ ) _1-4 Group, C═O group, Ph—C (CH ₃ ) ₂ Represents a group (where Ph represents a phenylene group), X ₇ Each independently represents a hydrogen atom or a methyl group, and n ₁₀ Represents an integer of 1 to 4 and n ₁₁ Represents an integer of 1 or 2, n ₁₂ Represents an integer of 1 to 3. )

The inorganic ultrafine particles are ultrafine particles having an average particle diameter of 1 to 200 nm containing one or more selected from metal chalcogenides or metal fluorides. Hard coat agent. In addition to components (A) and (B), the component (C) contains a urethane (meth) acrylate having two or more (meth) acryloyl groups. The hard coat agent described. A cured film with a film thickness of 2 μm applied to the surface of a resin having a thiourethane bond or an epithiosulfide bond and cured with ultraviolet rays,
[1] Cross-cut tape method peel test (JIS-K5400) has an evaluation score of 6 or more
[2] Pencil scratch test value (JIS-K5400) is 3H or more
The ultraviolet curable hard coat agent according to any one of claims 1 to 5, wherein The lens containing the hard-coat agent in any one of Claims 1-6.