JP2012041371A - Curable resin composition and molding - Google Patents

Abstract

A curable resin composition having optical properties, heat resistance and high moldability is provided.
A repeating unit (A) having a polymerizable unsaturated bond group, a repeating unit (B) having no polymerizable unsaturated bond, and a main chain of the repeating unit (B) are formed. A curable resin composition comprising a polymer (P) containing a repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group.
[Selection figure] None

Description

  The present invention relates to a curable resin composition and a molded body obtained by molding the curable resin composition. Furthermore, it is related with the manufacturing method of this molded object. In particular, it relates to a curable resin composition useful for the production of optical components.

Conventionally, curable resin compositions for producing optical components such as lenses have been employed. The curable resin composition used here is poured into a mold or the like and cured to be molded. It is also known that effective shrinkage is reduced by containing a polymer having a polymerizable group called a prepolymer in the curable resin composition.
As such a curable resin composition, the thing of patent document 1 and patent document 2 is known. The curable resin composition described in Patent Document 1 uses a urethane resin as a resin component. The curable resin composition described in Patent Document 1 has small shrinkage due to curing, good releasability, excellent scratch resistance, and excellent long-term stability at 60 ° C. However, there is a problem that the water absorption rate is high.
On the other hand, Patent Document 2 describes a curable resin composition containing adamantyl acrylate. The curable resin composition described in Patent Document 2 has high transparency. However, there is a problem that the glass transition temperature (Tg) is low.

JP-A-3-296513 JP 2006-213851 A

  An object of this invention is to provide the curable resin composition which can be used for preparation of an optical component etc., and has an optical characteristic, heat resistance, and high moldability.

  Under such circumstances, as a result of intensive studies by the inventor of the present application, a repeating unit (A) having a polymerizable unsaturated bond group, a repeating unit (B) having no polymerizable unsaturated bond, By using the polymer (P) containing the repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain of the repeating unit (B), Has been found to solve the problem, and the present invention has been completed. Specifically, it was achieved by the following means.

〔一般式（１）中、Ｒ¹は水素原子または置換基を表し、Ｌ¹は二価の連結基または単結合を表し、環αは単環式または多環式の環を表す。〕
（４）一般式（１）のαが炭素数５〜１５の炭素原子を骨格とする環状構造を含む繰返し単位である、（３）に記載の硬化性樹脂組成物。
（５）一般式（１）のαが、下記群（１）から選択される構造を骨格とする環状構造を含む繰返単位である、（３）に記載の硬化性樹脂組成物。
群（１）

（６）一般式（１）のＬ¹が、−ＣＯ−、−Ｏ−、−ＣＨ₂−及びこれらの組み合わせからなる基から選択される、（３）〜（５）のいずれか１項に記載の硬化性樹脂組成物。
（７）前記繰返単位（Ｂ）の主鎖を構成する重合性基とは異なる重合性基によって形成される主鎖を有する繰返単位（Ｃ）が、下記一般式（１）で表される繰返単位および下記一般式（２）で表される繰返単位の少なくとも１種類の繰返単位である、（１）〜（６）のいずれか１項に記載の硬化性樹脂組成物。

〔一般式（１）中、Ｒ¹は、水素原子または置換基を表し、Ｌ¹は二価の連結基または単結合を表し、環αは単環式または多環式の環を表す。〕

〔一般式（２）中、環βは単環式または多環式の環を表す。〕
（８）重合性不飽和結合基を有する繰返単位（Ａ）が、下記一般式（３）で表されることを特徴とする、（１）〜（７）のいずれか１項に記載の硬化性樹脂組成物。

〔一般式（３）中、Ｒ³〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表し、Ｌ³は二価の連結基または単結合を表す。〕
（９）２つ以上の重合性不飽和結合を有している化合物（Ｄ）が脂環構造を有していることを特徴とする（１）〜（８）のいずれか１項に記載の硬化性樹脂組成物。
（１０）１つの重合性不飽和基を有する化合物（Ｅ）が脂環構造を有していることを特徴とする（１）〜（９）のいずれか１項に記載の硬化性樹脂組成物。
（１１）重合体（Ｐ）の重量分子量が、５００〜１，０００，０００である、（１）〜（１０）のいずれか１項に記載の硬化性樹脂組成物。
（１２）重合体（Ｐ）が、重合性化合物を含む重合性組成物であって、該重合性化合物成分が、一般式（１）で表される繰返単位を構成する重合性化合物５〜８０質量％と、一般式（２）で表される繰返単位を構成する重合性化合物０〜５０質量％と、一般式（３）で表される繰返単位を構成する重合性化合物１０〜９０重量％と、他の重合性化合物５質量％以下のみからなる重合性組成物を用いて合成される、（８）〜（１１）のいずれか１項に記載の硬化性樹脂組成物。
（１３）重合体（Ｐ）の含有量が５〜６０質量％の範囲にあり、２つ以上の重合性不飽和結合を有している化合物（Ｄ）の含有量が２０〜９０質量％の範囲にあり、１つの重合性不飽和基を有する化合物（Ｅ）の含有量が２〜４０質量％の範囲にあり、他の成分の含量が５質量％以下であることを特徴とする（１）〜（１２）のいずれか１項に記載の硬化性樹脂組成物。
（１４）光または熱の照射により硬化を開始する開始剤（Ｆ）を少なくとも２種類以上有していることを特徴とする（１）〜（１３）のいずれか１項に記載の硬化性樹脂組成物。
（１５）重合体（Ｐ）の２％重量減少温度が２５０℃以上であることを特徴とする、（１）〜（１４）のいずれか１項に記載の硬化性樹脂組成物。
（１６）硬化後の波長５８９ｎｍにおける屈折率が１．４５以上であり、アッベ数が４５以上であり、波長５８９ｎｍにおける厚さ１ｍｍ換算の光線透過率が７５％以上であることを特徴とする（１）〜（１５）のいずれか１項に記載の硬化性樹脂組成物。
（１７）硬化後のガラス転移温度が２３０℃以上であることを特徴とする（１）〜（１６）のいずれか１項に記載の硬化性樹脂組成物。
（１８）（１）〜（１７）のいずれか１項に記載の硬化性樹脂組成物を成形してなることを特徴とする成形体。
（１９）空気中または窒素下で、３００℃、１０分保持しても、ひび割れを起こさない、（１８）に記載の成形体。
（２０）光学部品である、（１８）または（１９）に記載の成形体。
（２１）レンズ基材である、（１８）〜（２０）のいずれか１項に記載の成形体。
（２２）（１）〜（１７）のいずれか１項に記載の硬化性樹脂組成物を成形金型内において、二段階で硬化させることを特徴とする成形体の製造方法。 (1) Repeating unit (A) having a polymerizable unsaturated bond group, repeating unit (B) having no polymerizable unsaturated bond, and polymerization constituting the main chain of the repeating unit (B) A polymer (P) containing a repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group, and a compound (D) having two or more polymerizable unsaturated bonds, A curable resin composition comprising a compound (E) having one polymerizable unsaturated group.
(2) The curable resin composition according to (1), wherein the repeating unit (B) having no polymerizable unsaturated bond has an alicyclic structure.
(3) The curable resin composition according to (1) or (2), wherein the repeating unit (B) having no polymerizable unsaturated bond is represented by the following general formula (1): .
General formula (1)

[In General Formula (1), R ¹ represents a hydrogen atom or a substituent, L ¹ represents a divalent linking group or a single bond, and ring α represents a monocyclic or polycyclic ring. ]
(4) The curable resin composition according to (3), wherein α in the general formula (1) is a repeating unit including a cyclic structure having a carbon atom having 5 to 15 carbon atoms as a skeleton.
(5) The curable resin composition according to (3), wherein α in the general formula (1) is a repeating unit including a cyclic structure having a structure selected from the following group (1) as a skeleton.
Group (1)

(6) In any one of (3) to (5), L ^{1 in the} general formula (1) is selected from the group consisting of —CO—, —O—, —CH ₂ —, and combinations thereof. The curable resin composition described.
(7) The repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain of the repeating unit (B) is represented by the following general formula (1). The curable resin composition according to any one of (1) to (6), which is at least one type of repeating unit represented by the following repeating unit and the repeating unit represented by the following general formula (2).

[In General Formula (1), R ¹ represents a hydrogen atom or a substituent, L ¹ represents a divalent linking group or a single bond, and ring α represents a monocyclic or polycyclic ring. ]

[In general formula (2), ring β represents a monocyclic or polycyclic ring. ]
(8) The repeating unit (A) having a polymerizable unsaturated bond group is represented by the following general formula (3), according to any one of (1) to (7), Curable resin composition.

[In General Formula (3), R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent, and L ³ represents a divalent linking group or a single bond. ]
(9) The compound (D) having two or more polymerizable unsaturated bonds has an alicyclic structure, and is described in any one of (1) to (8) Curable resin composition.
(10) The curable resin composition according to any one of (1) to (9), wherein the compound (E) having one polymerizable unsaturated group has an alicyclic structure. .
(11) The curable resin composition according to any one of (1) to (10), wherein the polymer (P) has a weight molecular weight of 500 to 1,000,000.
(12) The polymer (P) is a polymerizable composition containing a polymerizable compound, and the polymerizable compound component comprises a polymerizable compound 5 constituting a repeating unit represented by the general formula (1). 80% by mass, 0-50% by mass of the polymerizable compound constituting the repeating unit represented by the general formula (2), and 10% of the polymerizable compound constituting the repeating unit represented by the general formula (3) The curable resin composition according to any one of (8) to (11), which is synthesized using a polymerizable composition consisting of 90% by weight and only 5% by mass or less of another polymerizable compound.
(13) The content of the polymer (P) is in the range of 5 to 60% by mass, and the content of the compound (D) having two or more polymerizable unsaturated bonds is 20 to 90% by mass. The content of the compound (E) having one polymerizable unsaturated group is in the range of 2 to 40% by mass, and the content of other components is 5% by mass or less (1 The curable resin composition according to any one of (12) to (12).
(14) The curable resin according to any one of (1) to (13), wherein the curable resin has at least two kinds of initiators (F) that start curing upon irradiation with light or heat. Composition.
(15) The curable resin composition according to any one of (1) to (14), wherein a 2% weight reduction temperature of the polymer (P) is 250 ° C. or higher.
(16) A refractive index at a wavelength of 589 nm after curing is 1.45 or more, an Abbe number is 45 or more, and a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 75% or more ( The curable resin composition according to any one of 1) to (15).
(17) The curable resin composition according to any one of (1) to (16), wherein the glass transition temperature after curing is 230 ° C. or higher.
(18) A molded article obtained by molding the curable resin composition according to any one of (1) to (17).
(19) The molded article according to (18), which does not crack even when held at 300 ° C. for 10 minutes in air or under nitrogen.
(20) The molded article according to (18) or (19), which is an optical component.
(21) The molded article according to any one of (18) to (20), which is a lens substrate.
(22) A method for producing a molded article, wherein the curable resin composition according to any one of (1) to (17) is cured in two stages in a molding die.

  According to the present invention, it is possible to provide a curable resin composition having optical properties, heat resistance, and high moldability.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Curable resin composition]
The curable resin composition of the present invention comprises a repeating unit (A) having a polymerizable unsaturated bond group, a repeating unit (B) having no polymerizable unsaturated bond, and the repeating unit (B). A curable resin composition comprising a polymer (P) containing a repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain of is there.

  In the curable resin composition of the present invention, the isolated polymer (P) may be dissolved, for example, in a compound having a polymerizable unsaturated group, or in a compound having a polymerizable unsaturated group. It may be prepared by synthesizing the union (P).

[Polymer (P)]
The polymer (P) used in the present invention comprises a repeating unit (A) having a polymerizable unsaturated bond group, a repeating unit (B) having no polymerizable unsaturated bond, and the repeating unit (B And a repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain.

〔一般式（３）中、Ｒ³〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表し、Ｌ³は二価の連結基または単結合を表す。〕
Ｒ³は、水素原子またはアルキル基が好ましく、水素原子または炭素数１〜４のアルキル基がより好ましく、水素原子またはメチル基がさらに好ましい。
Ｒ⁴およびＲ⁵は、それぞれ、水素原子またはアルキル基が好ましく、水素原子または炭素数１〜４のアルキル基がより好ましく、水素原子またはメチル基がさらに好ましく、水素原子が特に好ましい。
Ｒ⁶は、水素原子またはアルキル基が好ましく、水素原子または炭素数１〜４のアルキル基がより好ましく、水素原子またはメチル基がさらに好ましい。
Ｌ³は、−ＣＯ−、−Ｏ−、−ＣＨ₂−及びこれらの組み合わせからなる基から選択される二価の連結基であることが好ましい。Ｌ³は、−Ｃ（＝Ｏ）−Ｏ−で表される構造を有することがより好ましい。
一般式（３）で表される繰返単位は、通常、重合性化合物の重合によって得られる。かかる重合性化合物の分子量は、５０〜５００が好ましく、７０〜４００がより好ましく、９０〜３００がさらに好ましい。 Repeating unit having polymerizable unsaturated bond group (A)
The repeating unit (A) having a polymerizable unsaturated bond group in the present invention is characterized by having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group include an acryloyl group, a methacryloyl group, and a vinyl group. Or an allyl group, more preferably an acryloyl group, a methacryloyl group, or a vinyl group, and even more preferably an acryloyl group or a vinyl group.
The repeating unit (A) having a polymerizable unsaturated bond group is preferably represented by the general formula (3).

[In General Formula (3), R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent, and L ³ represents a divalent linking group or a single bond. ]
R ³ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
R ⁴ and R ⁵ are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
R ⁶ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
L ³ is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —CH ₂ —, and combinations thereof. L ³ more preferably has a structure represented by —C (═O) —O—.
The repeating unit represented by the general formula (3) is usually obtained by polymerization of a polymerizable compound. The molecular weight of the polymerizable compound is preferably 50 to 500, more preferably 70 to 400, and still more preferably 90 to 300.

  Specific examples of the monomer that can constitute the repeating unit (A) having a polymerizable unsaturated bond group are shown in the following A3-1 to A3-10, but the monomers that can be employed in the present invention are those It is not limited to a specific example.

〔一般式（１）中、Ｒ¹は水素原子または置換基を表し、Ｌ¹は二価の連結基または単結合を表し、環αは単環式または多環式の環を表す。〕 Repeating unit having no polymerizable unsaturated bond (B)
The repeating unit (B) having no polymerizable unsaturated bond preferably has an alicyclic structure, and more preferably has a structure represented by the following general formula (1). .
General formula (1)

[In General Formula (1), R ¹ represents a hydrogen atom or a substituent, L ¹ represents a divalent linking group or a single bond, and ring α represents a monocyclic or polycyclic ring. ]

上記環状構造は、置換基を有していても良いし、置換基を有していなくても良い。置換基を有している場合、アルキル基が好ましく、炭素数１〜３のアルキル基がより好ましく、メチル基がさらに好ましい。
一般式（１）で表される繰返単位は、通常、重合性化合物の重合によって得られる。かかる重合性化合物の分子量は、１００〜５００が好ましく、１００〜４００がより好ましく、１５０〜３００がさらに好ましい。 In general formula (1), R ¹ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a methyl group.
In general formula (1), L ¹ is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —CH ₂ — and combinations thereof, or a single bond, More preferred are divalent linking groups selected from the group consisting of —CO—, —O—, —CH ₂ —, and combinations thereof. L ¹ is preferably —C (═O) —O— on the side bonded to the main chain.
In general formula (1), α is preferably a cyclic structure having a carbon atom having 5 to 15 carbon atoms as a skeleton, and a cyclic structure having a structure selected from the following group (1) as a skeleton. More preferred.
Group (1)

The cyclic structure may have a substituent or may not have a substituent. When it has a substituent, an alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group is further more preferable.
The repeating unit represented by the general formula (1) is usually obtained by polymerization of a polymerizable compound. 100-500 are preferable, as for the molecular weight of this polymeric compound, 100-400 are more preferable, and 150-300 are further more preferable.

  Although the specific example of the polymeric compound which comprises the repeating unit represented by General formula (1) below is shown, the monomer which can be employ | adopted by this invention is not limited to these specific examples.

  In addition, as the repeating unit (B), a repeating unit represented by the general formula (2) described later and having no polymerizable group can be cited as a preferred example. As the repeating unit (B), the repeating unit represented by the general formula (1) is preferable.

〔一般式（２）中、環βは単環式または多環式の環を表す。〕
一般式（２）中、βは、炭素数５〜１０の炭素原子を骨格とする環状構造であり、下記群（２）から選択される構造を骨格とする環状構造であることがより好ましい。
群（２）

上記環状構造は、置換基を有していても良いし、置換基を有していなくても良い。置換基を有している場合、アルキル基、アリル基、オキソ基、ヒドロキシ基、シアノ基、ハロゲン原子が挙げられ、これらはさらにこれら基によって置換されていてもよい。また、置換基同士が結合して、環を形成していてもよい。置換基は、炭素原子、水素原子、酸素原子および窒素原子のいずれか１種以上から構成されることが好ましい。上記置換基は、炭素原子、酸素原子および窒素原子の合計原子数が、１〜１０個であることが好ましく、１〜５個であることがより好ましい。
一般式（２）で表される繰返単位は、通常、重合性化合物の重合によって得られる。かかる重合性化合物の分子量は、６０〜３００が好ましく、７０〜２５０がより好ましく、８０〜２００がさらに好ましい。 Repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain of the repeating unit (B)
The repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain of the repeating unit (B) in the present invention is usually the polymer (P ) Is obtained by polymerization of a polymerizable compound, but the type of the polymerizable group is different. Therefore, the formed main chain itself may be the same. In particular, in a preferred embodiment of the present invention, one of the polymerizable groups constituting the main chain of the repeating unit (B) and the repeating unit (C) is CH ₂ ═CH—, and the other is CH ₂ ═C ( This is the case for CH ₃ ) —.
Further, when two or more kinds of repeating units (B) having no polymerizable unsaturated bond are contained, a polymerizable group constituting one kind of the main chain and the main unit of the repeating unit (C) are included. It is sufficient that the polymerizable groups constituting the chain are different.
The repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain of the repeating unit (B) is a repeating unit represented by the general formula (1). Or it is especially preferable that it is a repeating unit represented by following General formula (2). However, when the repeating unit (C) is represented by the general formula (1) or the general formula (2), it is formed by a polymerizable group different from the polymerizable group constituting the main chain of the repeating unit (B). A repeating unit (C) having a main chain is selected. About the repeating unit represented by General formula (1), it is synonymous with the above-mentioned, and a preferable range is also synonymous. In the present invention, the repeating unit (C) is more preferably represented by the general formula (1).
Details of the general formula (2) will be described below.

[In general formula (2), ring β represents a monocyclic or polycyclic ring. ]
In general formula (2), β is a cyclic structure having a carbon atom having 5 to 10 carbon atoms as a skeleton, and more preferably a cyclic structure having a structure selected from the following group (2) as a skeleton.
Group (2)

The cyclic structure may have a substituent or may not have a substituent. When it has a substituent, an alkyl group, an allyl group, an oxo group, a hydroxy group, a cyano group, and a halogen atom are exemplified, and these may be further substituted with these groups. Moreover, substituents may couple | bond together and it may form the ring. The substituent is preferably composed of at least one of a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom. The total number of carbon atoms, oxygen atoms, and nitrogen atoms in the substituent is preferably 1 to 10, and more preferably 1 to 5.
The repeating unit represented by the general formula (2) is usually obtained by polymerization of a polymerizable compound. The molecular weight of the polymerizable compound is preferably 60 to 300, more preferably 70 to 250, and still more preferably 80 to 200.

  Hereinafter, preferred examples of the polymerizable compound constituting the repeating unit represented by the general formula (2) and other polymerizable compounds constituting the repeating unit (B) and / or the repeating unit (C) are shown. Needless to say, the present invention is not limited to these examples.

The polymer (P) can be usually synthesized by a known method using a polymerizable composition containing a polymerizable compound.
The polymerizable compound component contained in the polymerizable composition is composed of 10 to 90% by mass of a polymerizable compound constituting the repeating unit (A) having a polymerizable unsaturated bond group and a repeat having no polymerizable unsaturated bond. 5 to 80% by mass of the polymerizable compound constituting the returning unit (B) and a repeating unit having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain of the repeating unit (B) (C) It is preferably composed of 5 to 80% by mass and 5% by mass or less of other polymerizable compounds.
In the polymerizable compound component contained in the polymerizable composition, the polymerizable compound constituting the repeating unit (A) is preferably 20 to 90% by mass, and more preferably 20 to 80% by mass.
In the polymerizable compound component contained in the polymerizable composition, the polymerizable compound constituting the repeating unit (B) is preferably 10 to 80% by mass, and more preferably 10 to 70% by mass.
In the polymerizable compound component contained in the polymerizable composition, the polymerizable compound constituting the repeating unit (C) is preferably 10 to 80% by mass, and more preferably 10 to 70% by mass.

  As the repeating units represented by the general formula (1), the general formula (2), and the general formula (3), only one type may be used, or two or more types may be used in combination.

<Copolymerizable monomer>
The polymer (P) used in the present invention is represented by the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2), or the general formula (3) by polymerization. In addition to monomers capable of forming repeating units, other monomers may be copolymerized. As such other monomers, those described in Polymer Handbook 2nd ed., J. Brandrup, Wiley lnterscience (1975) Chapter 2 Page 1 to 483 can be used.

  Specifically, for example, styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, dialkyl itaconates And compounds having one addition polymerizable unsaturated bond selected from dialkyl esters or monoalkyl esters of fumaric acid.

  Examples of the styrene derivative include styrene, 2,4,6-tribromostyrene, 2-phenylstyrene, 4-chlorostyrene and the like.

  Examples of the acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, and benzyl acrylate. , Benzyl methacrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

  Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, and methoxy. Examples include benzyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate.

  Examples of the acrylamides include acrylamide, N-alkylacrylamide (alkyl group having 1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (alkyl group having 1 carbon atom). ~ 6), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

  Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), N, N-dialkyl methacrylamide (as alkyl groups). Are those having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.

  Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the dialkyl esters or monoalkyl esters of the fumaric acid include dibutyl fumarate.

  In addition, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile and the like can also be mentioned.

These polymers (P) may be used alone or in combination of two or more in the curable resin composition.
The number average molecular weight of the polymer (P) is preferably 500 to 1,000,000, more preferably 1,000 to 100,000, and further preferably 3,000 to 70,000. preferable.
The polymer (P) is preferably contained in the curable resin composition of the present invention in the range of 5 to 60% by mass, more preferably in the range of 7 to 50% by mass, and 10 to 40%. More preferably, it is contained in the range of mass%.

[Compound (D) having two or more polymerizable unsaturated groups]
The polymerizable unsaturated bond in the compound (D) having two or more polymerizable unsaturated groups that can be used in the present invention is preferably an acryloyl group, a methacryloyl group, a vinyl group, or an allyl group, An acryloyl group, a methacryloyl group, or a vinyl group is more preferable, and an acryloyl group or a vinyl group is more preferable.

The compound (D) having two or more polymerizable unsaturated groups that can be used in the present invention preferably has an alicyclic structure having 5 to 20 carbon atoms, and an alicyclic structure having 6 to 16 carbon atoms. It is more preferable that it has alicyclic structure having 6 to 10 carbon atoms. Further, a polycyclic alicyclic structure is more preferable.
The polymerizable unsaturated group and the alicyclic structure are preferably bonded directly or via a linking group, and are selected from the group consisting of —CO—, —O—, —CH ₂ — and combinations thereof. It is more preferably a divalent linking group, and further preferably a divalent linking group selected from the group consisting of —O—, —CH ₂ —, and combinations thereof.
The compound (D) having two or more polymerizable unsaturated groups preferably has two or three polymerizable unsaturated groups.
The molecular weight of the compound (D) having two or more polymerizable unsaturated groups is preferably 100 to 700, more preferably 130 to 600, and still more preferably 150 to 400.

  Specific examples of the compound (D) having two or more polymerizable unsaturated groups that can be used in the present invention are shown in the following D-1 to D-18, but the present invention is not limited thereto. Needless to say.

These compounds (D) having two or more polymerizable unsaturated groups may be used alone or in combination of two or more in the curable resin composition.
The compound (D) having two or more polymerizable unsaturated groups is preferably contained in the curable resin composition of the present invention in a range of 20 to 90% by mass, and in a range of 25 to 80% by mass. More preferably, it is more preferably included in the range of 30 to 70% by mass.

[Compound (E) having one polymerizable unsaturated group]
The polymerizable unsaturated bond in the compound (E) having one polymerizable unsaturated group that can be used in the present invention is preferably an acryloyl group, a methacryloyl group, a vinyl group, or an allyl group, and an acryloyl group. , A methacryloyl group or a vinyl group is more preferable, and an acryloyl group or a vinyl group is more preferable.

The compound (E) having one polymerizable unsaturated group that can be used in the present invention preferably has an alicyclic structure having 5 to 20 carbon atoms, and has an alicyclic structure having 6 to 16 carbon atoms. More preferably, it has an alicyclic structure having 6 to 10 carbon atoms. Further, a polycyclic alicyclic structure is more preferable.
The polymerizable unsaturated group and the alicyclic structure are preferably bonded directly or via a linking group, and are selected from the group consisting of —CO—, —O—, —CH ₂ — and combinations thereof. It is more preferably a divalent linking group, and further preferably a divalent linking group selected from the group consisting of —O—, —CH ₂ —, and combinations thereof.
The molecular weight of the compound (E) having one polymerizable unsaturated group is preferably 100 to 700, more preferably 150 to 600, and further preferably 200 to 500.

  Specific examples of the compound (E) having one polymerizable unsaturated group that can be used in the present invention are shown in the following E-1 to E-44, but it goes without saying that the present invention is not limited thereto. Nor.

As for the compound (E) having one polymerizable unsaturated group, only one kind may be used alone in the curable resin composition, or two or more kinds may be mixed and used.
It is preferable that the compound (E) which has one polymerizable unsaturated group is contained in the range of 0-40 mass% in the curable resin composition of this invention, and is contained in the range of 2-40 mass%. It is more preferable that it is contained in the range of 5 to 35% by mass.

[Initiator (F)]
The curable resin composition of the present invention may be cured by irradiation with active energy rays such as ultraviolet rays and electron beams, or may be cured by heating. Moreover, it is more preferable to harden by both light irradiation and heat irradiation.

  When curing by irradiation with active energy rays such as ultraviolet rays and electron beams, it is preferable to add a photopolymerization initiator. Known photopolymerization initiators can be used. Examples thereof include α-hydroxyalkylphenones, α-aminoalkylphenones, oxime esters, and acylphosphine oxides.

  When curing by heating, it is preferable to add a thermal polymerization initiator. A well-known thing can be used as a thermal-polymerization initiator. Examples thereof include azo compounds such as AIBN, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, and ketone peroxides.

  In the present invention, it is preferable to use a photopolymerization initiator and a thermal polymerization initiator in combination. It is more preferable to heat both after using both together and irradiating active energy rays. By adopting such means, it is semi-cured by irradiation with active energy rays in advance, so the amount of cure shrinkage in the mold is suppressed, and the mold shape transferability is excellent, and the mold The leakage to the gap (clearance) can be suppressed.

  0.001-5 mass% is preferable and, as for the content of the initiator in the curable resin composition of this invention, 0.1-3 mass% is preferable.

In addition to the above, other components can be added to the curable resin composition of the present invention without departing from the spirit of the present invention. For example, an antioxidant and a light stabilizer can be used. Specific examples of the antioxidant and the light stabilizer include those described in paragraph numbers 0022 to 0025 of JP-A-2006-231851. These components are preferably 5% by mass or less of the curable resin composition of the present invention.
It is preferable that the curable resin composition of the present invention does not substantially contain a solvent. “Substantially free” means, for example, that the content of the solvent is 1% by mass or less of the curable resin composition.

The curable resin composition of the present invention can be made liquid at 25 ° C. before curing.
The curable resin composition of the present invention can have a viscosity of 10 to 1,000,000 mPa · s, preferably 500 to 500,000 mPa · s, and more preferably at 25 ° C. before curing. 100 to 100,000 mPa · s.
The curable resin composition of the present invention can have a glass transition temperature (Tg) of 230 ° C. or higher, preferably 250 ° C. or higher, and more preferably 270 ° C. or higher. The upper limit value is not particularly defined, but can be, for example, 400 ° C. or lower.

In the curable resin composition of the present invention, the transmittance at a wavelength of 589 nm after curing can be 75% or more, preferably 80% or more, and more preferably 85% or more. it can.
In the curable resin composition of the present invention, the refractive index after curing at a wavelength of 589 nm can be 1.45 or more, and can be 1.50 or more. The upper limit is not particularly defined, but is usually 1.65 or less.
In the curable resin composition of the present invention, the Abbe number after curing can be 45 or more, and can be 50 or more. The upper limit is not particularly defined, but is usually 70 or less.

[Method for producing molded article]
As a method for producing a molded article such as an optical component using the curable resin composition of the present invention, a known method can be widely adopted. For example, it can be produced by filling a mold with the curable resin composition of the present invention and curing it by irradiation with active energy and / or heating. In the present invention, it is particularly preferable to use both active energy irradiation and heating. By adopting such means, the amount of cure shrinkage in the molding die is suppressed, so that the shape transferability of the die is excellent and the leakage to the gap (clearance) of the die can be suppressed.

[Use of molded body]
The molded body using the curable resin composition of the present invention is preferably used for an optical component and is preferably used for an optical lens.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

（５）吸水率測定
厚さ１ｍｍの基板状に成形した硬化物の重量（Ｗ_i）を測定し、を８５℃８５％ＲＨに設定した環境試験機中に一週間保持した後の硬化物の重量（Ｗ_f）を測定し、下記の式より算出した。

（６）ガラス転移温度測定
Ｒｈｅｏｇｅｌ−Ｅ４０００（株式会社ユービーエム製、動的粘弾性測定装置）を用いて、厚さ２００μｍ、幅５ｍｍ、長さ２３ｍｍの短冊フイルム状に成形した硬化物を引張りモード、周波数１０Ｈｚ、歪み１０μｍ（一定）の条件で、３０〜３００℃の温度範囲におけるｔａｎδを測定し、そのピーク温度をガラス転移温度（Ｔｇ）とした。３００℃までに明確なピークが存在しない場合、＞３００℃と表記した。
（７）成形性評価
硬化性樹脂組成物を成形金型内で硬化させ成形体を得る工程において、金型の隙間（クリアランス）へのモレの度合いを下記基準で評価した。成形を１０回おこなった後、モレが発生している個数が０個である場合を◎、１〜３個の場合を○、４〜８個の場合を△、８個以上の場合を×とした。
（８）耐加熱ひび割れ評価
厚さ１ｍｍの基板状に成形した硬化物(１水準あたり４枚)を、大気下、３００℃に加熱したホットプレート上に１０分保持し、ひび割れの状態を目視で判断した。
全サンプル無傷：◎
1〜2サンプル 小ヒビ：○
3〜4サンプル 小ヒビ：△
大きな亀裂・サンプル全面に及ぶヒビ：×
（９）加熱時アウトガス量評価
厚さ１ｍｍの基板状に成形した硬化物(１水準あたり４枚)を、大気下、３００℃に加熱したホットプレート上に１０分保持し、加熱前後の重量変化を測定した。 [Analysis and evaluation methods]
(1) Pyrolysis temperature measurement Using TG / DTA (Seiko Instruments (SII) EXSTAR6000, differential thermal and thermogravimetric simultaneous measurement), 5 mg of the powdered polymer was placed on a sample pan and heated at 50 to 400 ° C. The weight change in the area was observed.
(2) Measurement of light transmittance A cured product formed into a substrate having a thickness of 1 mm was prepared and measured for light having a wavelength of 589 nm using an ultraviolet-visible absorption spectrum measuring apparatus UV-3100 (manufactured by Shimadzu Corporation).
(3) Refractive index measurement It measured about the light of wavelength 589nm in the Abbe refractometer (Atago Co., Ltd. DR-M4).
(4) Abbe number (νD) measurement With an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.), the respective refractive indexes are measured for light with wavelengths of 486 nm, 589 nm, and 656 nm, and the refractive index at the wavelength of 486 nm is nF. When the refractive index at 589 nm was nD and the refractive index at a wavelength of 656 nm was nC, the calculation was performed according to the following formula.

(5) Measurement of water absorption rate The weight (W _i ) of the cured product formed into a substrate having a thickness of 1 mm was measured, and the cured product after being held for one week in an environmental tester set to 85 ° C. and 85% RH. The weight (W _f ) was measured and calculated from the following formula.

(6) Measurement of glass transition temperature Using a Rheogel-E4000 (manufactured by UBM Co., Ltd., dynamic viscoelasticity measuring device), a cured product formed into a strip film shape having a thickness of 200 μm, a width of 5 mm, and a length of 23 mm is pulled. Then, tan δ in a temperature range of 30 to 300 ° C. was measured under conditions of a frequency of 10 Hz and a strain of 10 μm (constant), and the peak temperature was defined as a glass transition temperature (Tg). When there was no clear peak up to 300 ° C, it was expressed as> 300 ° C.
(7) Moldability evaluation In the step of obtaining a molded body by curing the curable resin composition in a molding die, the degree of leakage into the gap (clearance) of the die was evaluated according to the following criteria. After molding 10 times, ◎ when the number of moles generated is 0, ◯ when 1-3, △ when 4-8, and x when 8 or more. did.
(8) Heat crack resistance evaluation A cured product (four per level) molded into a 1 mm thick substrate is held for 10 minutes on a hot plate heated to 300 ° C. in the atmosphere, and the state of cracks is visually observed. It was judged.
All samples intact: ◎
1-2 samples Small cracks: ○
3-4 samples Small cracks: △
Large cracks and cracks over the entire surface: ×
(9) Evaluation of outgas amount during heating Hold a cured product (4 per level) formed into a 1 mm thick substrate for 10 minutes on a hot plate heated to 300 ° C. in the atmosphere, and change in weight before and after heating Was measured.

(Preparation of materials)
(1) polymer Synthesis Example reflux condenser, a 1L three-necked flask equipped with a gas introduction cock, tricyclo [5,2,1,0 ^2,6] dec-8-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Product name FA-513M) 12.0g, tricyclo [5,2,1,0 ^2,6] deca-8-yl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name FA-513AS) 12.0g, allyl methacrylate ( Wako Pure Chemical Industries, Ltd.) 36.0 g and ethyl acetate 470.7 g were added, and after nitrogen substitution twice, Wako Pure Chemical Industries, Ltd., V-65 (trade name) 0.6 g was used as an initiator. After adding and replacing with nitrogen twice, the mixture was heated at 65 ° C. for 6 hours under a nitrogen stream. Thereafter, the reaction solution was poured into 2 L of methanol, and the precipitated white solid was collected by suction filtration. After drying under reduced pressure at 70 ° C. for 5 hours and distilling off the solvent, a polymer P-1 was obtained (yield 40%, number average molecular weight 45,800, weight average molecular weight 169,000). Other exemplified polymers can be prepared in a similar manner. The composition of the prepared polymer is shown in Table 1. The composition ratio is shown by weight%.

  As is apparent from Table 2, the polymer used in the present invention increases the thermal decomposition temperature of the polymer introduced into the curable resin composition.

(2) Preparation of curable resin composition The polymer shown in Table 1 was mixed and dissolved with various components in the composition shown in the following table to obtain a curable resin composition. In the following table, 1-hydroxycyclohexylphenone (manufactured by Wako Pure Chemical Industries, Ltd.) is represented as D-1, and cumene hydroperoxide (manufactured by NOF Corporation, trade name Park Mill H) is represented as D-2. In Comparative Example 1, the polymer (P) was not used, Polymer Q-1 was used in Comparative Example 2, and Polymer Q-2 was used in Comparative Example 3.

[Manufacture of optical components by ultraviolet light irradiation and heat compression]
Using the composition of each example and each comparative example, a lens was produced by the following procedure.
Arbitrary amount of the curable resin composition is put into a molding die (material; SUS304), 30 mW / cm ² of UV light is irradiated for 10 seconds from the opening portion using UL750 manufactured by HOYA, and semi-cured, Thereafter, the temperature was raised from room temperature to 200 ° C. at a rate of 10 ° C./min, and compression molding was performed at a pressure of 20 kgf to obtain a molded body. The cured product thus obtained was measured for light transmittance, refractive index, Abbe number, water absorption, and glass transition temperature. In addition, moldability was evaluated during molding. These results are listed in Table 3 below. Thereafter, the lens molding was molded into a lens shape to obtain a lens as an optical component.

  As is clear from the above table, by using the curable resin composition of the present invention, the moldability is good, the refractive index is greater than 1.45, the Abbe number is greater than 45, and the transparency is good. A good optical component having a low water absorption rate, a high glass transition temperature, a small amount of outgas even when heated, and no cracks in the molded product was obtained. On the other hand, in Comparative Example 1 in which the polymer (P) was not used, resin leakage occurred in all samples during molding, and the amount of outgas during heating was large, resulting in many cracks. In Comparative Example 2 in which Q-2 which does not contain a polymerizable unsaturated bond (B) and (C) is introduced, the Abbe number decreases, and the amount of outgas during heating is large. Large cracks occurred. In Comparative Example 1 in which Q-1 having no repeating unit (A) having a polymerizable unsaturated bond was introduced, the phase separation occurred after curing, so that the transmittance was greatly lowered and the glass transition temperature was also lowered. . In addition, the amount of outgas during heating was large, and small cracks were generated in the soot sample during heating.

Claims (22)

A repeating unit (A) having a polymerizable unsaturated bond group, a repeating unit (B) having no polymerizable unsaturated bond, and a polymerizable group constituting the main chain of the repeating unit (B); Is a polymer (P) containing a repeating unit (C) having a main chain formed by different polymerizable groups, a compound (D) having two or more polymerizable unsaturated bonds, and one A curable resin composition comprising a compound (E) having a polymerizable unsaturated group. The curable resin composition according to claim 1, wherein the repeating unit (B) having no polymerizable unsaturated bond has an alicyclic structure. The curable resin composition according to claim 1 or 2, wherein the repeating unit (B) having no polymerizable unsaturated bond is represented by the following general formula (1).
General formula (1)

[In General Formula (1), R ¹ represents a hydrogen atom or a substituent, L ¹ represents a divalent linking group or a single bond, and ring α represents a monocyclic or polycyclic ring. ] The curable resin composition according to claim 3, wherein α in the general formula (1) is a repeating unit including a cyclic structure having a carbon atom having 5 to 15 carbon atoms as a skeleton. The curable resin composition according to claim 3, wherein α in the general formula (1) is a repeating unit containing a cyclic structure having a structure selected from the following group (1) as a skeleton.
Group (1)

L ¹ in the general formula (1) is, -CO -, - O -, - CH 2 - is selected from the group consisting of an curable resin according to any one of claims 3 to 5 Composition. The repeating unit (C) having a main chain formed by a polymerizable group different from the polymerizable group constituting the main chain of the repeating unit (B) is represented by the following general formula (1). The curable resin composition according to any one of claims 1 to 6, which is at least one type of repeating unit represented by a unit and a repeating unit represented by the following general formula (2).

[In General Formula (1), R ¹ represents a hydrogen atom or a substituent, L ¹ represents a divalent linking group or a single bond, and ring α represents a monocyclic or polycyclic ring. ]

[In general formula (2), ring β represents a monocyclic or polycyclic ring. ] The curable resin composition according to any one of claims 1 to 7, wherein the repeating unit (A) having a polymerizable unsaturated bond group is represented by the following general formula (3). .

[In General Formula (3), R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent, and L ³ represents a divalent linking group or a single bond. ] The curable resin composition according to any one of claims 1 to 8, wherein the compound (D) having two or more polymerizable unsaturated bonds has an alicyclic structure. . The curable resin composition according to any one of claims 1 to 9, wherein the compound (E) having one polymerizable unsaturated group has an alicyclic structure. The curable resin composition of any one of Claims 1-10 whose weight molecular weights of a polymer (P) are 500-1,000,000. The polymer (P) is a polymerizable composition containing a polymerizable compound, and the polymerizable compound component constitutes a repeating unit represented by the general formula (1) in an amount of 5 to 80% by mass. And 0 to 50% by mass of the polymerizable compound constituting the repeating unit represented by the general formula (2), and 10 to 90% by weight of the polymerizable compound constituting the repeating unit represented by the general formula (3). The curable resin composition according to any one of claims 8 to 11, which is synthesized using a polymerizable composition comprising only 5% by mass or less of another polymerizable compound. The content of the polymer (P) is in the range of 5 to 60% by mass, and the content of the compound (D) having two or more polymerizable unsaturated bonds is in the range of 20 to 90% by mass. The content of the compound (E) having one polymerizable unsaturated group is in the range of 2 to 40% by mass, and the content of the other components is 5% by mass or less. The curable resin composition according to any one of the above. The curable resin composition according to any one of claims 1 to 13, comprising at least two kinds of initiators (F) that start curing upon irradiation with light or heat. The curable resin composition according to any one of claims 1 to 14, wherein a 2% weight reduction temperature of the polymer (P) is 250 ° C or higher. The refractive index at a wavelength of 589 nm after curing is 1.45 or more, the Abbe number is 45 or more, and the light transmittance in terms of 1 mm thickness at a wavelength of 589 nm is 75% or more. The curable resin composition according to any one of 15. The glass transition temperature after hardening is 230 degreeC or more, The curable resin composition of any one of Claims 1-16 characterized by the above-mentioned. A molded body obtained by molding the curable resin composition according to any one of claims 1 to 17. The molded article according to claim 18, which does not cause cracking even when held at 300 ° C for 10 minutes in air or nitrogen. The molded article according to claim 18 or 19, which is an optical component. The molded article according to any one of claims 18 to 20, which is a lens substrate. A curable resin composition according to any one of claims 1 to 17, which is cured in two stages in a molding die.