JP5513098B2 - Resin raw material composition for optical parts, resin for optical parts, and optical parts - Google Patents

Description

  The present invention has excellent transparency, does not generate cracks, has excellent shape stability, is stable against heat, does not cause yellowing, and has excellent releasability from the mold. The present invention relates to a raw material composition for producing a resin for parts, a resin for optical parts, and an optical part.

  Conventionally, as a transparent resin, a polymethyl methacrylate resin, a polycarbonate resin, a polystyrene resin, an alicyclic olefin polymer (for example, see Patent Document 1), an epoxy resin, and the like are known. These transparent resins are produced in large quantities industrially and are used in large quantities in various fields by taking advantage of their good transparency.

  Further, these transparent resins are used as glass substitutes by taking advantage of lightness and moldability in addition to their good transparency. Furthermore, the transparent resin is expected to be a material that can withstand the solder reflow process, reflecting the recent reduction in lightness, thinness, and reduction in the number of parts. To that end, in addition to optical characteristics such as light transmittance, High heat resistance is required.

  However, the above-described transparent resin does not necessarily have sufficient heat resistance. For example, among the above transparent resins, even a polycarbonate resin, which is considered to have the highest heat resistance, has a glass transition temperature of about 150 ° C., which is an index of heat resistance, and development of a new transparent resin having higher heat resistance. Is desired.

  Specifically, a poly (meth) acrylate polymer such as polymethyl methacrylate or a polycarbonate polymer has already been used for the resin material for optical parts as the transparent resin. However, polymethyl acrylate in the above poly (meth) acrylate polymer is inferior in performance such as heat resistance, heat stability, and solvent resistance, and has high water absorption and inferior water resistance. It cannot be used in the required fields. Polymethylmethacrylate is used for a resin material for optical parts, but cannot be applied to fields requiring extremely high heat resistance and heat stability that can withstand a solder reflow process.

  In the field of resin materials for optical parts, as a method for improving the above-mentioned problems of conventionally known poly (meth) acrylate polymers, homopolymers of polycyclic alicyclic alkyl (meth) acrylates, A method of using a copolymer of a polycyclic alicyclic alkyl (meth) acrylate and various (meth) acrylate monomers has been proposed (see, for example, Patent Documents 2 to 4).

These polycyclic alicyclic alkyl (meth) acrylate homopolymers and copolymers thereof described in Patent Documents 2 and 3 are both heat resistant and polymethyl (meth) acrylate as compared with polymethyl (meth) acrylates conventionally used. Although the heat resistance stability is improved, the improvement range is small, and the heat resistance that can withstand the solder reflow process is not reached. Patent Document 4 discloses adamantyl (meth) acrylate, but its heat resistance is insufficient for use in optical member applications, and deformation and breakage occur during the solder reflow process.
Therefore, in the field of resin materials for optical parts, there is a strong demand for the development of materials that are highly transparent, do not generate cracks, have excellent shape stability, and have excellent heat resistance and heat stability. Moreover, when manufacturing an optical component, the releasability of the optical component from the mold is important.

JP 2002-105131 A Japanese Patent Publication No. 7-17713 Japanese Patent Laid-Open No. 6-208001 JP 2006-213851 A

  The present invention has been made in view of the above situation, has excellent transparency, does not generate cracks, has excellent shape stability, is stable against heat and does not cause yellowing, An object of the present invention is to provide a raw material composition, an optical component resin, and an optical component for producing a resin for an optical component that is excellent in releasability from a mold during molding.

As a result of intensive studies to achieve the above object, the present inventors have found that a (meth) acrylate compound (A) having an adamantyl group and having a rigid site and a (meth) acrylate compound having a flexible site ( It has been found that a resin composition containing B) and an antioxidant (C) having a specific structure is suitable for the above purpose.
That is, the present invention provides the following resin raw material composition for optical parts, resin for optical parts, and optical parts.

1. The (meth) acrylate compound (A) represented by the following general formula (I), the (meth) acrylate compound (B) represented by the following general formula (II), and the fat represented by the following general formula (III) A group compound (C), and (1) the (meth) acrylate compound (A) includes a (meth) acrylate compound in which at least one X has an adamantyl group,
(2) The mass average molecular weight of the (meth) acrylate compound (B) is 140 to 2500, and (3) the ratio of the (meth) acrylate compound (A) to the (meth) acrylate compound (B) is 40 to 100% by mass: 60 to 0% by mass,
And (4) containing 0.01 to 10 parts by mass of the aliphatic compound (C) with respect to 100 parts by mass of the total amount of the (meth) acrylate compound (A) and the (meth) acrylate compound (B),
A resin raw material composition for optical parts.

（Ｘは多環式脂肪族炭化水素基、芳香族炭化水素基又は単環式脂肪族炭化水素基、Ｙは独立に直接結合、炭素数１〜４のアルキレン基又は炭素数１〜４のオキシアルキレン基、Ｒ¹は独立に水素原子又はメチル基であり、ｎは１〜４の整数である。）

(X is a polycyclic aliphatic hydrocarbon group, aromatic hydrocarbon group or monocyclic aliphatic hydrocarbon group, Y is independently a direct bond, an alkylene group having 1 to 4 carbon atoms, or an oxy group having 1 to 4 carbon atoms. An alkylene group, R ¹ is independently a hydrogen atom or a methyl group, and n is an integer of 1 to 4.)

〔Ｚ¹は、エーテル結合を含んでも良い炭素数５〜３０の非環状炭化水素基及び／又は-Ｒ³(ＯＲ³)ｋ-で表されるオキシアルキレン基（Ｒ³は炭素数１〜４の鎖状アルキレン基を含む有機置換基、ｋは１〜２０の整数である。）、Ｒ²は独立に水素原子又はメチル基であり、ｍは１〜８の整数である。〕

[Z ¹ is an acyclic hydrocarbon group having 5 to 30 carbon atoms which may contain an ether bond and / or an oxyalkylene group represented by —R ³ (OR ³ ) k— (wherein R ³ has 1 to 4 carbon atoms) An organic substituent containing a linear alkylene group, k is an integer of 1 to 20), R ² is independently a hydrogen atom or a methyl group, and m is an integer of 1 to 8. ]

[Ｒ⁴は炭素数６〜３０の脂肪族炭化水素基、Ｗは水素原子、金属原子又は炭素数１〜８の炭化水素基である。]

[R ⁴ is an aliphatic hydrocarbon group having 6 to 30 carbon atoms, W is a hydrogen atom, a metal atom, or a hydrocarbon group having 1 to 8 carbon atoms. ]

（Ｚ²は、エーテルを含んでも良い炭素数１〜３０の直鎖状又はエーテル結合を含んでも良い炭素数３〜３０の分岐状脂肪族炭化水素基、単環式又は多環式脂肪族炭化水素基、および芳香族炭化水素基から選ばれる一種以上の有機基、Ｙ¹はエーテル結合を含んでも良い炭素数５〜３０の非環状炭化水素基、Ｒ⁵は独立に炭素数１〜４のアルキレン基を示し、ｐは２〜２０の整数である。Ｒ²およびｍは前式と同様である。） 2. The resin raw material composition for optical components according to 1 above, wherein the (meth) acrylate compound (B) is a compound represented by the following general formula (IV) or general formula (V).

(Z ² is a C1-C30 straight chain which may contain ether or a C3-C30 branched aliphatic hydrocarbon group which may contain an ether bond, monocyclic or polycyclic aliphatic carbonization. One or more organic groups selected from a hydrogen group and an aromatic hydrocarbon group, Y ¹ is an acyclic hydrocarbon group having 5 to 30 carbon atoms that may contain an ether bond, and R ⁵ is independently an alkyl group having 1 to 4 carbon atoms. Represents an alkylene group, and p is an integer of 2 to 20. R ² and m are the same as in the previous formula.)

3. In the (meth) acrylate compound (B) represented by the general formula (IV), Y ¹ is an alkylene group represented by — (CH ₂ ) r— or — (CH ₃ CH) r— (r is 5 to 30). 2) or a propylene group represented by-(CR ⁶ -CR ⁷ ) q- (wherein either R ⁶ or R ⁷ is a hydrogen atom and the other is a methyl group, q is an integer of 2 to 15). A resin raw material composition for optical parts.
4). The resin raw material composition for optical parts according to any one of 1 to 3, wherein 20 to 100% by mass of the (meth) acrylate compound (A) is a (meth) acrylate compound having an adamantyl group.
5. In the (meth) acrylate compound (A) represented by the general formula (I), the ratio in which n is 1 and n is 2 to 4 is 50 to 0% by mass: 50 to 100% by mass The resin raw material composition for optical components in any one of 1-4.
6). M in the (meth) acrylate compound (B) represented by the general formula (II) is an integer of 4 to 8, the molecular weight of Z ¹ is 400 or less, and the number of carbon atoms that may contain an ether bond in Z ¹ An acyclic hydrocarbon group having 5 to 30 and an oxyalkylene group represented by —R ³ (OR ³ ) k— (R ³ is an organic substituent containing a chain alkylene group having 1 to 4 carbon atoms, k is 1 to The resin raw material composition for optical components according to any one of 1 to 5 above, containing 15 to 50% by mass of an organic group other than 20).

7). 7. The resin raw material composition for optical parts according to any one of 1 to 6 above, wherein the melting point of the aliphatic compound (C) is in the range of −40 to 140 ° C.
8). 8. The resin raw material composition for optical parts according to any one of 1 to 7 above, wherein W of the aliphatic compound (C) is a hydrogen atom, and R ⁴ is an aliphatic hydrocarbon group having 6 to 20 carbon atoms.
9. 8. The resin raw material composition for optical components according to any one of 1 to 7 above, wherein W of the aliphatic compound (C) is a metal atom, and R ⁴ is an aliphatic hydrocarbon group having 6 to 18 carbon atoms.
10 Aliphatic Compound (C) W is a hydrocarbon group, and the total number of carbon atoms of R ⁴ and the hydrocarbon group of W is 7-30. .
11. The optical component according to any one of 1 to 10 above, containing 0.01 to 10 parts by mass of an antioxidant with respect to 100 parts by mass of the total amount of the (meth) acrylate compound (A) and the (meth) acrylate compound (B). Resin raw material composition.
12 The resin for optical components obtained by superposing | polymerizing the resin raw material composition for optical components in any one of said 1-11.
13. 13. An optical component obtained by molding the resin for optical components according to 12 above.

  According to the present invention, it has excellent transparency, does not generate cracks, has excellent shape stability, is stable against heat, does not cause yellowing, and can be released from a mold during molding. In addition, it is possible to provide a raw material composition, an optical component resin, and an optical component from which an excellent optical component resin can be obtained.

The resin raw material composition for optical parts of the present invention includes a (meth) acrylate compound (A) represented by the following general formula (I) and a (meth) acrylate compound (B) represented by the general formula (II). It contains. The “(meth) acrylate compound” indicates that both an acrylate compound and a methacrylate compound are included.
Next, each component of the resin raw material composition for optical parts of the present invention will be described.

（Ｘは、多環式脂肪族炭化水素基、芳香族炭化水素基又は単環式脂肪族炭化水素基、Ｙは独立に、直接結合、炭素数１〜４のアルキレン基又は炭素数１〜４のオキシアルキレン基、Ｒ¹は独立に水素原子又はメチル基であり、ｎは１〜４の整数である。）

(X is a polycyclic aliphatic hydrocarbon group, aromatic hydrocarbon group or monocyclic aliphatic hydrocarbon group, Y is independently a direct bond, an alkylene group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. And R ¹ is independently a hydrogen atom or a methyl group, and n is an integer of 1 to 4.)

〔Ｚ¹は、エーテル結合を含んでも良い炭素数５〜３０の非環状炭化水素基及び／又は-Ｒ³(ＯＲ³)ｋ-で表されるオキシアルキレン基（Ｒ³は炭素数１〜４の鎖状アルキレン基を含む有機置換基、ｋは１〜２０の整数である。）、Ｒ²は独立に水素原子又はメチル基であり、ｍは１〜８の整数である。〕

[Z ¹ is an acyclic hydrocarbon group having 5 to 30 carbon atoms which may contain an ether bond and / or an oxyalkylene group represented by —R ³ (OR ³ ) k— (wherein R ³ has 1 to 4 carbon atoms) An organic substituent containing a linear alkylene group, k is an integer of 1 to 20), R ² is independently a hydrogen atom or a methyl group, and m is an integer of 1 to 8. ]

In the resin raw material composition for optical parts of the present invention, the (meth) acrylate compound (A) is mainly a hard segment in the resin for optical parts, and when polymerized, it is in a site having low mobility between molecules. Become.
First, in the (meth) acrylate compound (A) represented by the general formula (I), the polycyclic aliphatic hydrocarbon group represented by X includes a decahydronaphthyl group, a norbornyl group, a 1-methyl-norbornyl group, 5 , 6-dimethyl-norbornyl group, isobornyl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecyl group, 9-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecyl group, dicyclopentanyl group, tricyclopentanyl group and adamantyl group represented by the following general formula.

上式中、Ｕは炭素数１〜４のアルキル基、ハロゲン原子、水酸基又は、２つのＵが一緒になって形成された＝Ｏを示す。ｋは０〜１５の整数を示す。また、複数のＵは同じでもよく、異なっていてもよい。
これらの中で、ジシクロペンタニル基、１−アダマンチル基が好ましく、特に１−アダマンチル基が好適である。なお、上記例示の各基は、モノイル基のみならず、ジイル基、トリイル基およびテトライル基を包含する。

In the above formula, U represents an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, or ═O formed by combining two U together. k represents an integer of 0 to 15. The plurality of U may be the same or different.
Among these, a dicyclopentanyl group and a 1-adamantyl group are preferable, and a 1-adamantyl group is particularly preferable. In addition, each group of the said illustration includes not only a monoyl group but a diyl group, a triyl group, and a tetrayl group.

The (meth) acrylate compound represented by the general formula (I) may be a single type or a combination of two or more types.
The (meth) acrylate compound (A) represented by the general formula (I) is a (meth) acrylate compound in which 20 to 100% by mass of the (meth) acrylate compound (A) has an adamantyl group from the viewpoint of heat resistance. (See Examples 17-24).
In the general formula (I), examples of the compound containing an adamantyl group and n is 1 include adamantylmethanol (meth) acrylate and adamantylethanol (meth) acrylate.

Examples of the compound in which n is 2 include adamantyl dimethanol di (meth) acrylate and adamantyl diethanol di (meth) acrylate.
Examples of the compound in which n is 3 include adamantyltrimethanol tri (meth) acrylate and adamantyltriethanol tri (meth) acrylate.

Y is independently a direct bond, an alkylene group having 1 to 4 carbon atoms, an oxyalkylene group having 1 to 4 carbon atoms, or an alkylene group, specifically, —C—, —CC—, —CCC—, — CCCC-, -C (C) -C-, -C (C ₂ ) -C-, etc., and specific examples of oxyalkylene groups include -CO-, -CCO-, -CC (C) -O- , -CCCO-, -CCCCO-, -CCOC-, -COC-, etc.
Since the X and Y moieties correspond to hard segment sites when polymerized, X must be a polycyclic aliphatic hydrocarbon group, an aromatic hydrocarbon group or a monocyclic aliphatic hydrocarbon group. Is a direct bond, an alkylene group having 4 or less carbon atoms, or an oxyalkylene group having 4 or less carbon atoms.

  In the (meth) acrylate compound (A), the ratio of the (meth) acrylate compound containing an adamantyl group is preferably 20 to 100% by mass, and more preferably 30 to 100% by mass. By setting the ratio to 20% by mass or more, discoloration with respect to heat can be suppressed.

Examples of the aromatic hydrocarbon group include a biphenyl group, a phenyl group, a naphthyl group, an anthracene group, a bisphenol group, and residues of the following aromatic hydrocarbon compounds. In addition, each group of the said illustration includes not only a monoyl group but a diyl group, a triyl group, and a tetrayl group.

Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexyl group, a cyclobutyl group, a cyclopentyl group, a cycloheptyl group, and a cyclooctyl group.
In addition, each group of the said illustration includes not only a monoyl group but a diyl group, a triyl group, and a tetrayl group.
As described above, (meth) acrylate compounds in which X is an aromatic hydrocarbon group or a monocyclic aliphatic hydrocarbon group include bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and tricyclodecanedi. Examples include methanol di (meth) acrylate, alkoxylated cyclohexanedimethanol di (meth) acrylate, and alkoxylated bisphenol A di (meth) acrylate.

In the general formula (I), the (meth) acrylate compound (A) needs to have a ratio of 50 to 0% by mass: 50 to 100% by mass where n is 1 and n is 2 to 4. It is preferable that the ratio is 40 to 0% by mass: 60 to 100% by mass.
When the ratio of n in the general formula (I) is 50% by mass or less, an optical resin excellent in shape stability without cracking after thermal history can be obtained. When X is only an adamantyl group, or when n is only 1, heat resistance and stability are affected.

The (meth) acrylate compound (B) is a (meth) acrylate compound represented by the following general formula (II), which may be one kind or a combination of two or more kinds, and from the viewpoint of crosslinking density, m Is preferably a compound having 2 or more.
The (meth) acrylate compound (B) has a mass average molecular weight of 140 to 2500, preferably 190 to 2000. If the weight average molecular weight of the (meth) acrylate compound (B) exceeds 2500, the shape may change after the heat history.

〔Ｚ¹は、エーテル結合を含んでも良い炭素数５〜３０の非環状炭化水素基及び／又は-Ｒ³(ＯＲ³)ｋ-で表されるオキシアルキレン基（Ｒ³は炭素数１〜４の鎖状アルキレン基を含む有機置換基、ｋは１〜２０の整数である。）、Ｒ²は独立に水素原子又はメチル基であり、ｍは１〜８の整数である。〕

[Z ¹ is an acyclic hydrocarbon group having 5 to 30 carbon atoms which may contain an ether bond and / or an oxyalkylene group represented by —R ³ (OR ³ ) k— (wherein R ³ has 1 to 4 carbon atoms) An organic substituent containing a linear alkylene group, k is an integer of 1 to 20), R ² is independently a hydrogen atom or a methyl group, and m is an integer of 1 to 8. ]

Z ¹ of the (meth) acrylate compound (B) is an acyclic hydrocarbon group having 5 to 30 carbon atoms and an oxyalkylene group represented by —R ³ (OR ³ ) k— that may contain the ether bond. In addition, the straight chain hydrocarbon group having less than 5 carbon atoms, a branched hydrocarbon group, a monocyclic or polycyclic aliphatic hydrocarbon group, an aromatic hydrocarbon group and the like are included. May be.
An acyclic hydrocarbon group having 5 to 30 carbon atoms and an oxyalkylene group represented by —R ³ (OR ³ ) k—, which may contain an ether bond, serve as a soft segment in the resin for optical components. A soft segment (a site having many so-called flexible sites) has a high mobility in the polymer chain in the molecule and becomes a flexible site.

（Ｚ²は、エーテル結合を含んでも良い炭素数１〜３０の直鎖状又はエーテル結合を含んでも良い炭素数３〜３０の分岐状炭化水素基、単環式又は多環式脂肪族炭化水素基、および芳香族炭化水素基から選ばれる一種以上の有機基、Ｙ¹はエーテル結合を含んでも良い炭素数５〜３０の非環状炭化水素基、Ｒ⁵は独立に炭素数１〜４のアルキレン基を示し、ｐは２〜２０の整数である。Ｒ²およびｍは前式と同様である。） Further, when Z ^{1 of} the (meth) acrylate compound (B) is an acyclic hydrocarbon group having 5 to 30 carbon atoms which may contain an ether bond, the following general formula (IV) is preferable. Or when Z ^{1 of the} (meth) acrylate compound (B) is an oxyalkylene group represented by —R ³ (OR ³ ) k—, it is a compound represented by the following general formula (V) Is preferred.

(Z ² is a C1-C30 straight chain which may contain an ether bond or a C3-C30 branched hydrocarbon group which may contain an ether bond, a monocyclic or polycyclic aliphatic hydrocarbon. And one or more organic groups selected from an aromatic hydrocarbon group, Y ¹ is an acyclic hydrocarbon group having 5 to 30 carbon atoms which may contain an ether bond, and R ⁵ is independently an alkylene having 1 to 4 carbon atoms And p is an integer of 2 to 20. R ² and m are the same as in the previous formula.)

The monocyclic or polycyclic aliphatic hydrocarbon group of Z ² and the aromatic hydrocarbon group are the same as described in the general formula (I). Further, the alkylene group having 1 to ⁴ carbon atoms of R ⁴ is the same as described in the general formula (I).
The C1-C30 linear aliphatic hydrocarbon group that may contain an ether bond of Z ² represents an alkylene group or an oxyalkylene group. The alkylene group and oxyalkylene group are the same as those described for Y in formula (I).
The branched aliphatic hydrocarbon group having 3 to 30 carbon atoms which may contain an ether bond of Z ² is isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group. And an isohexyl group. An ether bond may be included between the carbons.

Specific examples of the acyclic hydrocarbon group for Y ¹ include an alkylene group represented by — (CH ₂ ) r—, — (CH ₃ CH) r— (wherein r is an integer of 5 to 30), — ( CR ⁵ —CR ⁶ ) q-represented propylene group [wherein either R ⁵ or R ⁶ is a hydrogen atom and the other is a methyl group, q is an integer of 2 to 15], — (CH ₂ O) r—, — An alkoxy group represented by (CH ₃ CHO) r— [r is an integer of 5 to 30] and the like.
Furthermore, Y ^{1 of the} (meth) acrylate compound (B) represented by the above general formula (IV) is a linear alkylene group (r is an integer of 5 to 30) represented by — (CH) r— or The compound is preferably a propylene group represented by-(CR ⁵ -CR ⁶ ) q- (wherein either R ⁵ or R ⁶ is a hydrogen atom and the other is a methyl group, q is an integer of 2 to 15).

  Examples of the (meth) acrylate compound represented by the general formula (IV) and m = 2 are 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,12-dodecanediol dimethacrylate (manufactured by Sartomer Japan KK), polybutadiene di (meth) acrylate, hydrogenated polybutadiene di (meth) acrylate, and the like.

  Examples of the (meth) acrylate compound represented by formula (IV) and having m of 3 or more include pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and polyfunctional polyester (meth) acrylate.

  Examples of the (meth) acrylate compound represented by the general formula (V) in which m is 2 include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) having a p of 2 to 20. ) Acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, alkoxylated neopentyl glycol diacrylate, tetraethylene glycol di (meth) acrylate, alkoxylated cyclohexane Examples thereof include diol diacrylate (manufactured by Sartomer Japan Co., Ltd.). Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate having a p of 2 to 20 are preferable.

Examples of the (meth) acrylate compound represented by the general formula (V) in which m is 3 or more include ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and p is 2 to 2. 20 alkoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glyceryl tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, alkoxylated glyceryl tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, Propoxylated pentaerythritol tetra (meth) acrylate, alkylated trimethylolpropane tri (meth) acrylate, alkoxylated pentaerythritol tetra (meth) acrylate with p of 2-20, ethoxylated dipe Taerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, alkylated dipentaerythritol hexa (meth) acrylate, p = 2 to 20 alkoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated di Pentaerythritol penta (meth) acrylate, propoxylated dipentaerythritol penta (meth) acrylate, alkylated dipentaerythritol hexa (meth) acrylate, alkoxylated dipentaerythritol penta (meth) acrylate with p of 2 or more, alkylated dipenta Examples include erythritol penta (meth) acrylate.
In the compound in which m in the (meth) acrylate compound (B) represented by the general formula (II) is an integer of 4 to 8, the molecular weight of Z ¹ is 400 or less, and Z ¹ may contain an ether bond. An acyclic hydrocarbon group having 5 to 30 carbon atoms and an oxyalkylene group represented by —R ³ (OR ³ ) k— (R ³ is an organic substituent containing a chain alkylene group having 1 to 4 carbon atoms, k is A (meth) acrylate compound which is an organic group other than 1 is an integer of 1 to 20.

  The resin raw material composition for optical parts of the present invention is composed of 40 to 100% by mass of compound (A) and 60 to 0% by mass of compound (B) with respect to the total amount of compound (A) and compound (B). It needs to be. It is preferable that a compound (A) is 45-100 mass%, a compound (B) is 55-0 mass%, a compound (A) is 50-100 mass%, and a compound (B) is 50-0 mass%. More preferably. When the amount of the compound (A) is 40% by mass or more, the effect of addition is obtained, deformation and discoloration with respect to heat are suppressed, and the moisture content is low with a low linear expansion coefficient.

The aliphatic compound (C) represented by the general formula (III) imparts releasability to the (meth) acrylate compound (A) and the (meth) acrylate compound (B).
The aliphatic compound (C) is dissolved in the (meth) acrylate compound (A) or the (meth) acrylate compound (B), and is well dispersed. It is easy to move, and when it is cured, it is ejected from the resin component that is cured, and is present between the mold and the curing component so that it has releasability. In addition, when the mold is released, the release property can be further improved by having a low viscosity in a molten state.
From the above points, the aliphatic compound (C) preferably has a melting point in the range of −40 ° C. to 140 ° C., and more preferably in the range of −30 ° C. to 130 ° C. By setting the melting point of the aliphatic compound (C) to −40 ° C. or higher, good releasability is exhibited without causing vaporization at the time of curing and generating bubbles or the like in the product to cause poor appearance. In addition, when the melting point of the aliphatic compound (C) is 140 ° C. or lower, the solubility is improved and good appearance and releasability are obtained.

The aliphatic hydrocarbon group of R ⁴ of the aliphatic compound (C) represented by the general formula (III) may have a linear structure or a branched structure, and the bonding state in the molecular chain may be only a single bond, Multiple bonds may be included. Specifically, it is an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group. The number of multiple bonds in the aliphatic unsaturated hydrocarbon group may be one or more.
The hydrocarbon group of R ⁴ has 6 to 30 carbon atoms. If the number of carbon atoms is less than 6, it will volatilize at the time of curing, and the aliphatic compound (C) cannot be present between the mold and the material, so that the releasability does not appear, or there are bubbles in the material. May remain. When the number of carbon atoms is larger than 30, the mobility of the material becomes low, and the aliphatic compound (C) is taken into the material and the material becomes opaque, or the releasability is not expressed. The carbon number of the hydrocarbon group for R ⁴ is preferably 6 to 26, more preferably 8 to 22.

Examples of the metal atom in W of the aliphatic compound (C) represented by the general formula (III) include alkali metals such as lithium and sodium, alkaline earth metals such as magnesium and calcium, and aluminum. In the case of Group 2 or aluminum, since it is divalent or more, the general formula of the aliphatic compound (C) is represented by (R ⁴ —CO—O) _ql W, and q is 2 to 4.

  The hydrocarbon group in W of the aliphatic compound (C) represented by the general formula (III) may be a linear structure or a branched structure, and the bonding state in the molecular chain may be only a single bond or multiple bonds. It may be included. Specifically, it is an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group. The number of multiple bonds in the aliphatic unsaturated hydrocarbon group may be one or more. The hydrocarbon group of W has 1 to 8 carbon atoms. When the number of carbon atoms is 9 or more, the melting point and solubility of the aliphatic compound (C) are increased, and the aliphatic compound (C) is incorporated into the resin component during curing or is unevenly distributed. The pattern may not appear or may become opaque. The preferable carbon number of the hydrocarbon group of W is 1-6.

In order to express good releasability, when W of the aliphatic compound (C) represented by the general formula (III) is a hydrogen atom, R ⁴ is aliphatic carbonization having 6 to 20 carbon atoms. A hydrogen group is preferred. When W is a metal atom, R ⁴ is preferably an aliphatic hydrocarbon group having 6 to 18 carbon atoms. When W is a hydrocarbon group, the total number of carbon atoms of R ⁴ and the hydrocarbon group of W is preferably 7-30.

  The content of the aliphatic compound (C) in the resin raw material composition for optical parts of the present invention is based on 100 parts by mass of the total amount of the (meth) acrylate compound (A) and the (meth) acrylate compound (B). It is 0.01-10 mass parts, Preferably it is 0.01-5 mass parts. When the content of the aliphatic compound (C) exceeds 10 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylate compound (A) and the (meth) acrylate compound (B), The shape stability against heat may not be maintained. If it is less than 0.01 parts by mass, releasability cannot be obtained.

  The resin raw material composition for optical parts of the present invention contains an antioxidant as necessary. Examples of antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, thioether antioxidants, vitamin antioxidants, lactone antioxidants, and amine antioxidants. .

  Examples of phenolic antioxidants include Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1076 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1330 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Trademark), Irganox 3114 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 3125 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO-20 (ADEKA Corporation, trademark), ADK STAB AO-50 (trademark) ADEKA Co., Ltd.), Adeka Stub AO-60 (ADEKA Co., Ltd.), Adeka Stub AO-80 (ADEKA Co., Ltd.), Adeka Stub AO-30 (ADEKA Co., Ltd.), Adeka Stub AO-40 (Stock) Formula company ADEKA, trademark), BHT (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), Cyanox 1790 (trade name, manufactured by Cyanamid Co., Ltd.), Sumitizer GP (trademark, manufactured by Sumitomo Chemical Co., Ltd.), Sumizer GM (produced by Sumitomo Chemical Co., Ltd. Trademarks), Sumilizer GS (trademark, manufactured by Sumitomo Chemical Co., Ltd.) and Sumilizer GA-80 (trademark, manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of phosphorus compounds include IRAGAFOS 168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS 12 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS 38 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS P-EPQ (trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS126 (trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.), ADKSTAB 329K (ADEKA, trade mark), ADKSTAP PEP-36 (trade mark) ADEKA, trademark), ADKSTAP PEP-8 (ADEKA, trademark), ADKSTAB HP-10 (ADEKA, trademark), ADKSTAB 2112 (ADEKA, trademark), ADK STAB 260 (ADEKA, trademark), ADKSTAB 522A (ADEKA, trademark), Weston 618 (GE, trademark), Weston 619G (GE, trademark), and Weston 624 (GE, trademark) And other commercial products.

Examples of sulfur-based antioxidants include DSTP (Yoshitomi) (trademark), DLTP (Yoshitomi) (trademark, produced by Yoshitomi Corporation), DLTOIB (trademark, produced by Yoshitomi Corporation), DMTP (Yoshitomi). ) [Trademark] made by Yoshitomi Co., Ltd., Seenox 412S [trademark made by Sipro Kasei Co., Ltd.], Cyanox 1212 (trademark made by Cyanamid Co., Ltd.) and TP-D, TPS, TPM, TPL-R [Sumitomo Chemical Co., Ltd. ), Trade mark, etc.).
Examples of vitamin-based antioxidants include tocopherol (trade name, manufactured by Eisai Co., Ltd.) and Irganox E201 (trade name, compound name: 2,5,7,8-tetramethyl-2 (4, manufactured by Ciba Specialty Chemicals Co., Ltd.). Commercial products such as ', 8', 12'-trimethyltridecyl) coumarone-6-ol].

Examples of the thioether-based antioxidant include commercially available products such as ADK STAB AO-412S (trade name, manufactured by ADEKA Corporation) and ADK STAB AO-503 (trade name, manufactured by ADEKA Corporation).
As the lactone antioxidant, those described in JP-A-7-233160 and JP-A-7-247278 can be used. Moreover, HP-136 [Ciba Specialty Chemicals Co., Ltd., trademark, compound name; 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one] And other commercial products.

Examples of amine-based antioxidants include commercially available products such as Irgastab FS042 [trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.] and GENOX EP [trade name, compound name; dialkyl-N-methylamine oxide] manufactured by Crompton Co., Ltd. Can do.
These antioxidants can be used singly or in combination of two or more.

  The content of the antioxidant is usually 0.01 with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B) from the viewpoint of suppressing the transparency of the resin material for optical parts and the reduction of yellowing. -10 mass parts, preferably 0.01-5 mass parts, more preferably 0.02-2 mass parts.

The resin raw material composition for optical parts of the present invention (hereinafter also referred to as “raw material composition”) may contain a radical polymerization initiator as required.
Examples of thermal radical polymerization initiators that generate initiation radicals by cleavage by heat include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1 Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and t-butyl hydroperoxide; diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide Diacyl peroxides such as oxide, benzoyl peroxide and m-toluyl benzoyl peroxide; dicumyl peroxide, 2, 5 Dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, di-t-butyl peroxide and 2,5-dimethyl- Dialkyl peroxides such as 2,5-di (t-butylperoxy) hexene; 1,1-di (t-butylperoxy-3,5,5-trimethyl) cyclohexane, 1,1-di-t-butylperoxy Peroxyketals such as cyclohexane and 2,2-di (t-butylperoxy) butane; 1,1,3,3-tetramethylbutylperoxyneodicarbonate, α-cumylperoxyneodicarbonate, t-butylperoxyneodicarbonate , T-hexylperoxypivalate, t-butylperoxypivalate 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butyl Peroxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, 1,1,3,3-tetramethylbutylperoxy-3,5,5-trimethylhexanate, t-amylperoxy-3,5,5-trimethyl Alkyl peresters such as hexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and dibutylperoxytrimethyladipate; di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexyl Ruperoxydicarbonate, bis (1,1-butylcyclohexaoxydicarbonate), diisopropyloxydicarbonate, t-amylperoxyisopropylcarbonate, t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexylcarbonate and 1, Peroxycarbonates such as 6-bis (t-butylperoxycarboxy) hexane; 1,1-bis (t-hexylperoxy) cyclohexane and (4-t-butylcyclohexyl) peroxydicarbonate.

As the radical polymerization initiator, in addition to the thermal radical polymerization initiator, a radical polymerization initiator that generates an initiation radical by light, electron beam, or radiation can be used.
Examples of such radical polymerization initiators include benzoin ether, 2,2-dimethoxy-1,2-diphenylethane-1-one [IRGACURE651, manufactured by Ciba Specialty Chemicals Co., Ltd.], 1-hydroxy-cyclohexyl. -Phenyl-ketone [IRGACURE184, manufactured by Ciba Specialty Chemicals Co., Ltd., trademark], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [DAROCUR1173, manufactured by Ciba Specialty Chemicals Co., Ltd., Trademarks], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [IRGACURE2959, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2 -Hydroxy-1- [4- [4- (2-H Roxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one [IRGACURE127, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropan-1-one [IRGACURE907, manufactured by Ciba Specialty Chemicals, Inc.], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 [ IRGACURE 369, manufactured by Ciba Specialty Chemicals, Inc., trademark], 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-monophorinyl) phenyl] -1-butanone [IRGACURE 379, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.] 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCUR TPO, manufactured by Ciba Specialty Chemicals, Inc.], bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [IRGACURE819, Ciba Specialty Chemicals, Inc., Trademark], bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Titanium [IRGACURE784, trade name, manufactured by Ciba Specialty Chemicals, Inc.], 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] [IRGACURE OXE 01, Ciba Specialty Chemicals, Inc., trademark], ETA 1,1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) [IRGACURE OXE 02, manufactured by Ciba Specialty Chemicals Co., Ltd. , Trademark] and the like.
These radical polymerization initiators can be used singly or in combination of two or more.

  The usage-amount of a radical polymerization initiator is about 0.01-10 mass parts normally with respect to 100 mass parts of total amounts of a compound (A) and a compound (B), Preferably it is 0.05-5 mass parts. In the case of initiating polymerization by heat, the raw material composition containing a radical polymerization initiator can be usually polymerized by heating to about 40 to 200 ° C. In the case of initiating polymerization by light, polymerization can be performed by irradiating the raw material composition with ultraviolet light or visible light using a mercury xenon lamp or the like as a light source.

In addition to the above antioxidant, the raw material composition of the present invention includes a lubricant, a light stabilizer, an ultraviolet absorber, a plasticizer, an antistatic agent, an inorganic filler, a colorant, and an antistatic agent as necessary. , Mold release agents, flame retardants, components for the purpose of improving adhesion with inorganic compounds such as titanium oxide and silicon oxide, and the like can be blended.
As the lubricant, higher dicarboxylic acid metal salts, higher carboxylic acid esters, and the like can be used.

Any known light stabilizer can be used, but a hindered amine light stabilizer is preferred. Specific examples of the hindered amine light stabilizer include ADKSTAB LA-77, LA-57, LA-52, LA-62, LA-67, LA-68, LA-63, and LA-94. LA-94, LA-82 and LA-87 (above, manufactured by ADEKA Corporation), Tinuvin 123, 144, 440 and 662, Chimassorb 2020, 119, 944 (above, manufactured by CSC), Examples include Hostavin N30 (manufactured by Hoechst), Cyasorb UV-3346, UV-3526 (manufactured by Cytec), Uval 299 (GLC), and SanduvorPR-31 (Clariant).
These light stabilizers can be used singly or in combination of two or more.

The usage-amount of a light stabilizer is 0.005-5 mass parts normally with respect to 100 mass parts of total amounts of a compound (A) and a compound (B), Preferably it is 0.02-2 mass parts. .
Examples of the component for improving the adhesion with inorganic compounds such as titanium oxide and silicon oxide include silane coupling agents containing a methacryloxy group or an acryloxy group of the silane compound. This may be contained in the raw material composition, and the optical component may be polymerized and molded.

  The optical component of the present invention can be produced by polymerizing and molding the above raw material composition. In the polymerization of the raw material composition, preliminary polymerization may be performed by adding the radical polymerization initiator to the monomer component containing the compound (A) as a main component. By performing such preliminary polymerization, the viscosity of the raw material composition can be adjusted.

  As the polymerization / molding method, the same method as that for molding a normal thermosetting resin can be used. For example, the above raw material composition or a prepolymer thereof may be used for polymerization / molding by injection molding, compression molding, transfer molding, insert molding, etc. of these liquid resins. Moreover, a molded object can also be obtained by a potting process or a coating process. Furthermore, a molded body can be obtained by a method similar to the molding of a photo-curing resin such as UV curing molding.

  The optical component of the present invention is preferably manufactured by a liquid resin molding method. Liquid resin molding methods include liquid resin injection molding in which a raw material composition that is liquid at room temperature or a prepolymer thereof is pressed into a high-temperature mold and heat-cured, and a liquid raw material composition is placed in a mold and pressed by a press. Examples thereof include compression molding for pressing and curing, transfer molding for curing the raw material composition by applying pressure to the heated liquid raw material composition and press-fitting it into a mold.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
In the following Examples and Comparative Examples, the obtained resins were evaluated as follows (including a heat test).

(1) Presence / absence of cracks after thermal history Using a plate-like body having a thickness of 2 mm, a length of 25 mm, and a width of 25 mm of the resin obtained in the examples and comparative examples, the three plate-like bodies are stainless steel plates of 3 mm thickness. The plate was allowed to stand at 250 ° C. for 10 minutes, and then the presence or absence of cracks in the plate was confirmed and evaluated according to the following criteria.
○: There are no cracks.
Δ: The number of cracks having a length of 10 mm or more was 2 or less,
Or the length of all the cracks is less than 10 mm.
X: Cracks having a length of 10 mm or more occurred in all three sheets.

(2) Evaluation of shape stability after heat history Using a plate-like body having a thickness of 2 mm, a length of 25 mm, and a width of 25 mm as described above, the three plate-like bodies were placed on a stainless steel plate having a thickness of 3 mm, and 250 After leaving at 10 ° C. for 10 minutes, the degree of deformation of the edge of the plate was visually confirmed and evaluated according to the following criteria.
○: The edge portion is the same as before the heat history, and the shape stability is excellent.
Δ: The edge portion is partially rounded, and the shape stability is normal.
X: The edge portion is uniformly rounded and inferior in shape stability.

(3) Light transmittance It measured based on JISK7105 using the test piece of thickness 3mm (unit%). As a measuring device, HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.) was used. The measurement was performed before placing the test piece in the oven (initial characteristics) and after placing the test piece in an oven at 250 ° C. for 10 minutes (after the heat resistance test).
The light transmittance was evaluated as follows.
(A) Initial total light transmittance: light transmittance (%) before placing the test piece in the oven
(B) Decrease in total light transmittance (Δ250 ° C. total light transmittance): difference between the initial light transmittance and the total light transmittance after being placed in an oven at 250 ° C. for 10 minutes (after the heat resistance test) Absolute value(%)

(4) Yellowing degree (YI value)
The YI value was measured using an SZ optical SENSOR (manufactured by Nippon Denshoku Industries Co., Ltd.) using a test piece measuring 30 mm long × 30 mm wide × 3 mm thick.
The yellowing degree (YI value) was evaluated as follows.
(A) Initial yellowing degree (initial YI value): YI value before putting a test piece into the oven (b) Amount of decrease in YI value (Δ0 ° C. YI value): In the oven at 250 ° C. with the initial YI value Absolute value of difference in YI value after 10 minutes (after heat test)

(5) Solubility A liquid containing 0.1 g of C2 component is prepared for 10 g of adamantane acrylate compound. The solution is stirred at room temperature for 20 minutes. If not dissolved, it may be heated in the range up to an upper limit temperature of 80 ° C. Leave at room temperature for 60 minutes, and evaluate the solubility from the liquid state at that time.
Judgment of solubility was made ◯ when the solution was colorless and transparent, △ when the solution was not colorless and transparent but had no precipitate and suspended, and x otherwise.

(6) Releasability In molding methods A and B, which will be described later, five cured products are prepared, and after curing, the stainless steel plate is removed, and the releasability is evaluated from the degree of adhesion with the cured product when the stainless steel sheet is taken out. did. In molding method C, after the mold was opened, the releasability was evaluated from the resistance when the flat plate was taken out from the mold.
The evaluation of releasability was judged by two people, and the judgment criteria were as follows.
(In the case of molding methods A and B)
○: When the stainless steel sheet was peeled off from the cured product, both of them could peel off without resistance.
(Triangle | delta): When peeling the stainless steel sheet from hardened | cured material, only one person was able to peel off without a feeling of resistance.
X: When peeling a stainless steel sheet from hardened | cured material, both had resistance. Or the sticking remains on the sheet.
(Curing method C)
○: When taking out the cured product from the mold, both of them did not feel resistance, and the molded product stuck to the mold could be taken out without being cracked in a state of sticking to the mold.
(Triangle | delta): When taking out hardened | cured material from a metal mold | die, only one person did not have a sense of resistance, and the molded article sticking to the metal mold | die could be taken out without cracking in the state stuck to the metal mold | die.
X: When taking out hardened | cured material from a metal mold | die, both had resistance. Or when taking out, the hardened | cured material was cracked because the mold stuck.

In Examples and Comparative Examples, the molding method was performed as follows.
(Forming method A)
Two stainless steel plates with a thickness of 3 mm and a length of 70 mm each are sandwiched between two stainless steel plates with a thickness of 0.1 m and a thickness of 70 mm. Resin was molded using a container obtained by sandwiching a 70 mm Teflon (registered trademark) spacer.
The liquid raw material composition was poured into the above container to obtain a cured product. The Teflon (registered trademark) spacer section is 3 mm thick and has a 30 mm vertical and horizontal window and a passage through which the raw material composition can be poured into the window. The container is heated in an oven under a nitrogen atmosphere (oxygen concentration of 5% or less) at 110 ° C. for 3 hours, then at 160 ° C. for 1 hour, polymerized and molded, and then cooled to room temperature to be colorless and transparent A plate was obtained.
When the product surface was not flat due to sink, it was polished with sandpaper or an abrasive to make the surface flat and used for evaluation of optical properties.
(Forming method B)
It was carried out in the same manner as the molding method A except that the curing temperature was 100 ° C. for 3 hours and then 160 ° C. for 1 hour.
(Forming method C)
The raw material composition was polymerized and molded using a liquid resin sealing device (manufactured by Apic Yamada) to obtain a plate-like cured product. The size of the cured product was a flat plate having a thickness of 2 mm, a length of 50 mm, and a width of 50 mm.
The mold surface is plated with hard chrome. The polymerization and molding conditions were a mold temperature of 140 ° C. and a curing time of 3 minutes. The holding pressure at the time of curing was 5 MPa, and the obtained cured product was heated at 160 ° C. for 1 hour and gradually cooled at room temperature to obtain a colorless and transparent plate.

Production Example 1 (Synthesis of 1,3-adamantane dimethanol dimethacrylate)
To a 2000 ml 4-necked flask equipped with a stirring blade, a Dean-Stark cooler, a temperature indicator, and a three-way cock, 1,3-adamantane dimethanol [100 g, 0.51 mol], methacrylic acid [110.2 g, 1. 28 mol], 98 mass% sulfuric acid [4.60 g, 0.046 mol], methoquinone [0.092 g, 1000 wtppm with respect to acrylic acid] and 1000 mL of toluene were added.
The flask was heated and stirred in an oil bath at 130 ° C., and the reaction was carried out for 3 hours while removing water from the reaction system by azeotropy. After cooling to near room temperature, the mixture was transferred to a separatory funnel and washed in the order of 5% by mass NaCl aqueous solution, 5% by mass Na ₃ PO ₄ aqueous solution, and 5% by mass NaCl aqueous solution. The organic layer was separated, dehydrated with magnesium sulfate, and toluene was distilled off at 40 ° C. to obtain 1,3-adamantanedimethanol dimethacrylate represented by the following chemical formula (yield 86%, GC purity 97% by mass) )

Reference Examples 1-8
30 parts by mass of 1-adamantyl methacrylate [Osaka Organic Chemical Co., Ltd.] represented by the following chemical formula as compound (A) and tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester A-DCP) ) 70 parts by mass, 0.5 parts by mass of each of the aliphatic compounds (C1) to (C8) shown in Table 1 below as the compound (C), and Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.) as the antioxidant 0.5 parts by mass) and 0.4 parts by mass of Perhexa HC (Nippon Yushi Co., Ltd.) as a polymerization initiator were added and mixed to obtain a raw material composition. This raw material composition was molded into a shape suitable for the above-described evaluation method using molding method A. The evaluation results are shown in Table 1.

Examples 9-16
30 parts by mass of 1-adamantyl methacrylate and 45 parts by mass of tricyclodecane dimethanol diacrylate (A-DCP) as the compound (A) and 24 parts by mass of SR-499 (manufactured by Saitomer Japan Co., Ltd.) as the compound (B) The procedure was the same as in Reference Examples 1 to 8, except that no antioxidant was used. The evaluation results are shown in Table 2.

Examples 17-24
Example 9 to Example 9 except that 45 parts by mass of tricyclodecane dimethanol dimethacrylate (DCP) was used instead of tricyclodecane dimethanol diacrylate (A-DCP) and 0.5 parts by mass of Irganox 1076 was used as an antioxidant. This was carried out in the same manner as in 16. The evaluation results are shown in Table 3.

Examples 25-32
Examples 17 to 24 except that 45 parts by mass of 1,3-adamantane dimethanol diacrylate obtained in Production Example 1 was used instead of 45 parts by mass of tricyclodecane dimethanol dimethacrylate (DCP) of compound (A). As well as. The evaluation results are shown in Table 4.

Examples 33-40
The same as in Examples 9 to 16 except that 0.5 parts by mass of Irganox 1076 as an antioxidant and 0.4 parts by mass of Parroyl L (manufactured by NOF Corporation) as a polymerization initiator were used and the molding method B was used. It was. The evaluation results are shown in Table 5.

Reference Examples 41-48
Only 50 parts by mass of 1-adamantyl methacrylate as the compound (A), 40 parts by mass of SR-502 (manufactured by Saitomer Japan Co., Ltd.) and 10 parts by mass of SR-399 (manufactured by Saitomer Japan Ltd.) as the compound (B) The procedure was the same as in Reference Examples 1 to 8, except that was used. The evaluation results are shown in Table 6.

Reference Examples 49-56
Instead of SR-502 of the compound (B), SR-415 [Sitemer Japan K.K.
[Production] The same procedure as in Reference Examples 41 to 48 was conducted, except that 40 parts by mass were used. The evaluation results are shown in Table 7.

Examples 57-64
The same procedure as in Examples 9 to 16 except that 1.0 part by mass of perhexa HC was used as a polymerization initiator and the molding method C was used. The evaluation results are shown in Table 8.

Comparative Example 1
The same procedure as in Examples 9 to 16 except that 0.5 part by mass of Irganox 1076 was used as an antioxidant and the aliphatic compound (C) was not used. The evaluation results are shown in Table 9.

Comparative Example 2
The same procedure as in Examples 9 to 16 except that 0.5 part by mass of Irganox 1076 was used as an antioxidant and 0.5 alcohol (Calcoal 0898) 0.5 was used instead of the aliphatic compound (C). The evaluation results are shown in Table 9.

Comparative Example 3
Except not using the aliphatic compound (C), it was the same as Examples 17-24. The evaluation results are shown in Table 9.

Comparative Example 4
Except not using an aliphatic compound (C), it was the same as that of Examples 25-32. The evaluation results are shown in Table 9.

Comparative Example 5
It was the same as Reference Examples 41 to 48 except that the aliphatic compound (C) was not used. The evaluation result is 9
Shown in the table.

Comparative Example 6
It was the same as Reference Examples 41 to 48 except that 0.5 part of higher alcohol B (Calcoal 8098) was used instead of the aliphatic compound (C). The evaluation results are shown in Table 9.

As is clear from the above examples and comparative examples, in all examples of the present invention, there is no generation of cracks after the thermal history, the shape stability is excellent, the transparency is excellent and stable, and the initial yellowing occurs. It can be seen that even when heated at a low degree (YI value), the increase in YI value is extremely small and the mold release property is excellent. Some fatty acid metal salts have low solubility, but do not adversely affect transparency and releasability.
On the other hand, in the comparative example, there is no occurrence of cracks after the heat history, and it is found that although the shape stability, transparency, and yellowing degree (YI value) are excellent, the releasability is poor.
In the present invention, when the aliphatic compound (C) is present in the raw material composition (curing liquid), a component having no (meth) acrylate compound (A) and (meth) acrylate compound (B) reaction site at the time of curing. Curing while excluding, the aliphatic compound (C) is unevenly distributed between the mold and the cured product. Since this aliphatic compound (C) is composed of an oil and fat component, it is considered that it effectively acts as a mold release agent when taking out the cured product from the mold.

The compound names and chemical formulas of the raw materials and polymerization initiator used in each Example and Comparative Example are as follows.
Compound (A)
(1) A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical)
Compound name: Tricyclo [5.2.1.0 (2,6)] decane-3,8 (or 3,9 or 4,8) -diyldimethyl diacrylate

(2) DCP: Tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical)
Compound name: Tricyclo [5.2.1.0 (2,6)] decane-3,8 (or 3,9 or 4,8) -diyldimethyl dimethacrylate

Compound (B)
(1) SR-499: Ethoxylation (6) Trimethylolpropane triacrylate [manufactured by Sartomer Japan KK, CAS. 28961-43-5, existing chemical substance 7-775, average molecular weight 560]
Compound name: 8- [7- (acryloyloxy) -2,5-dioxaheptane] -8-ethyl-3,6,10,13-tetrapentadecane-1,15-diyl diacrylate

(2): SR-399: Dipentaerystol pentaacrylate [manufactured by Sartomer Japan, Inc., average molecular weight 525]
Compound name: 2- (acryloyloxy) methyl-2-({2,2-bis [(acryloyloxy) methyl] -3-hydroxypropan-1-yl] oxy} methylpropane-1,3-diyl = diacrylate

(3) SR-502: Ethoxylation (9) Trimethylolpropane triacrylate [Sartomer Japan, Inc., average molecular weight 692]
Compound name: 11- [10- (acryloyloxy) -2,5,8-trioxadecan-1-yl] -11-ethyl-3,6,9,13,16,19-hexaoxahenicosane- 1,2-diyl diacrylate

(4) SR-415: Ethoxylation (20) Trimethylolpropane triclarate [Sartomer Japan, Inc., average molecular weight 1176]
Compound name: 20-ethyl-20- (21-oxo-2,5,8,11,14,17,20-heptaoxatricos-22-enyl) -3,6,9,12,15,18, 22,25,28,31,34,37-dodecaoxanonatriacontane-1,39-diyl diacrylate

Polymerization initiator (1) Perhexa HC (manufactured by NOF Corporation)
Compound name: 1,1-di (t-hexylperoxy) cyclohexane

(2) Parroyl L (Nippon Yushi Co., Ltd.)
Chemical formula: Dilauroyl peroxide

Table 10 shows the compound names and chemical formulas of the aliphatic compound (C) and the aliphatic compound (C ′) similar thereto.

Claims (10)

A resin raw material composition for optical parts molded by a liquid resin molding method,
The (meth) acrylate compound (A) represented by the following general formula (I), the (meth) acrylate compound (B) represented by the following general formula (II), and the fat represented by the following general formula (III) A group compound (C), and (1) the (meth) acrylate compound (A) includes a (meth) acrylate compound in which at least one X has an adamantyl group,
(2) In the (meth) acrylate compound (A), the ratio of n = 1 to n = 2-4 is 50-0% by mass: 50-100% by mass,
( 3 ) The mass average molecular weight of the (meth) acrylate compound (B) is 140 to 2500,
( 4 ) The ratio of the (meth) acrylate compound (A) and the (meth) acrylate compound (B) is 40 to 75 % by mass: 60 to 25 % by mass,
And ( 5 ) 0.01-10 mass parts of aliphatic compounds (C) are contained with respect to 100 mass parts of total amounts of (meth) acrylate compound (A) and (meth) acrylate compound (B),
A resin raw material composition for optical parts.

(X is a polycyclic aliphatic hydrocarbon group, aromatic hydrocarbon group or monocyclic aliphatic hydrocarbon group, Y is independently a direct bond, an alkylene group having 1 to 4 carbon atoms, or an oxy group having 1 to 4 carbon atoms. An alkylene group, R ¹ is independently a hydrogen atom or a methyl group, and n is an integer of 1 to 4.)

[Z ¹ is an acyclic hydrocarbon group having 5 to 30 carbon atoms which may contain an ether bond and / or an oxyalkylene group represented by —R ³ (OR ³ ) k— (wherein R ³ has 1 to 4 carbon atoms) An organic substituent containing a linear alkylene group, k is an integer of 1 to 20), R ² is independently a hydrogen atom or a methyl group, and m is an integer of 1 to 8. ]

[R ⁴ is an aliphatic hydrocarbon group having 6 to 30 carbon atoms, W is a hydrogen atom, a metal atom, or a hydrocarbon group having 1 to 8 carbon atoms. ] The resin raw material composition for an optical component according to claim 1, wherein 20 to 100% by mass of the (meth) acrylate compound (A) is a (meth) acrylate compound having an adamantyl group. M in the (meth) acrylate compound (B) represented by the general formula (II) is an integer of 4 to 8, the molecular weight of Z ¹ is 400 or less, and the number of carbon atoms that may contain an ether bond in Z ¹ An acyclic hydrocarbon group having 5 to 30 and an oxyalkylene group represented by —R ³ (OR ³ ) k— (R ³ is an organic substituent containing a chain alkylene group having 1 to 4 carbon atoms, k is 1 to It is an integer of 20. The resin raw material composition for optical components of Claim 1 or 2 containing 15-50 mass% of organic groups other than. The resin raw material composition for an optical component according to any one of claims 1 to 3 , wherein the melting point of the aliphatic compound (C) is in the range of -40 to 140 ° C. The resin raw material composition for an optical component according to any one of claims 1 to 4 , wherein W of the aliphatic compound (C) is a hydrogen atom, and R ⁴ is an aliphatic hydrocarbon group having 6 to 20 carbon atoms. The resin raw material composition for an optical component according to any one of claims 1 to 4 , wherein W of the aliphatic compound (C) is a metal atom, and R ⁴ is an aliphatic hydrocarbon group having 6 to 18 carbon atoms. The resin material for an optical component according to any one of claims 1 to 4 , wherein W of the aliphatic compound (C) is a hydrocarbon group, and the total number of carbon atoms of the hydrocarbon groups of R ⁴ and W is 7 to 30. Composition. The total amount of 100 parts by mass of the (meth) acrylate compound (A) (meth) acrylate compound (B), according to any one of claims 1 to 7, containing 0.01 to 10 parts by weight of antioxidant A resin raw material composition for optical parts. The resin for optical components obtained by superposing | polymerizing the resin raw material composition for optical components in any one of Claims 1-8 . An optical component obtained by molding the resin for optical components according to claim 9 .