WO2013129345A1

WO2013129345A1 - (meth)acrylate-based composition, resin, and molded article

Info

Publication number: WO2013129345A1
Application number: PCT/JP2013/054832
Authority: WO
Inventors: 寛小幡; 猛岩崎; 大地小川; 勇人山崎; 東洋藏藤岡; 智明武部
Original assignee: 出光興産株式会社
Priority date: 2012-02-29
Filing date: 2013-02-25
Publication date: 2013-09-06
Also published as: TW201402623A; CN104136471A; KR20140130686A

Abstract

This (meth)acrylate-based composition comprising a (meth)acrylate compound (A) that has an adamantyl group represented by general formula (A-1) and a (meth)acrylate compound (B) that has a specific structure in a single molecule has excellent workability because the composition has high viscosity while maintaining good heat resistance, shape stability, and optical performance, such as refractive index and transparency. (In formula (A-1): each R¹ independently represents a hydrogen atom or a methyl group; each X independently represents a single bond, a C_1-4 alkylene group, or a C_1-4 oxyalkylene group; U represents a C_1-4 alkyl group, a halogen group, a hydroxyl group, or =O formed by linking two Us; k represents an integer from 0 to 15; and m represents an integer from 1 to 4.)

Description

(Meth) acrylate composition, resin, and molded article

The present invention relates to a (meth) acrylate composition, a resin obtained by polymerizing the composition, and a molded body obtained by molding the resin. Specifically, a (meth) acrylate-based composition that is a resin raw material composition for optical parts, including a (meth) acrylate compound having an adamantyl group, a resin for optical parts obtained by polymerizing the composition, and the resin The present invention relates to an optical component formed by molding.

As the transparent resin, polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, alicyclic olefin polymer, 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.

In addition to its good transparency, transparency resin is used as a substitute for glass by taking advantage of its light weight and formability, and it can be applied to lenses for camera modules mounted on camera phones. It has been. Here, reflecting the recent miniaturization and reduction in the number of parts, a transparent resin that can withstand the solder reflow process is desired. To that end, in addition to optical characteristics such as light transmittance, extremely high heat resistance Sex is required.
However, the above-described transparent resin does not necessarily have sufficient heat resistance. For example, among the above transparent resins, even the polycarbonate resin, which is the most heat-resistant resin, 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.

Polymethyl acrylate, which is known as a transparent resin, is inferior in performance such as heat resistance, heat stability, and solvent resistance, and has high water absorption and poor water resistance. It cannot be used in certain fields. Polymethylmethacrylate is used for a resin material for optical parts, but cannot be applied to fields that require extremely high heat resistance and heat stability that can withstand a solder reflow process.

As a method for improving such a problem, a polycyclic alicyclic alkyl (meth) acrylate homopolymer, a polycyclic alicyclic alkyl (meth) acrylate and various (meth) acrylate monomers A method using a resin composition for an optical material containing a copolymer has been proposed (see, for example, Patent Document 1). The material disclosed in Patent Document 1 is excellent in heat resistance while maintaining excellent transparency.

JP 2006-215081 A

Such an optical component is produced through a manufacturing process in which a liquid composition at room temperature is placed in a mold and cured by heating, pressurizing, or the like. At this time, if the viscosity of the liquid composition used as the raw material of the optical component is small, the composition leaks from the clearance between the mold and the tool when the composition is injected into the mold and pressurized. May end up. Such an adverse effect can be prevented by using a mold having a special structure. However, there is a demand for a method of manufacturing an optical component that can prevent the phenomenon that the composition leaks from the clearance without using such a special mold.

When a special mold is not used, it is conceivable to increase the viscosity of the composition in order to prevent the phenomenon of the composition leaking from the clearance. As a means of increasing the viscosity of the composition, a method of increasing the molecular weight of each component contained in the composition can be considered, but if the molecular weight of each component is increased, the crosslinking reaction at the time of curing hardly proceeds, and the cured product obtained Since the crosslinking density of the cured product becomes low, the heat resistance and shape stability of the cured product, and the optical performance such as the refractive index and transparency often deteriorate. Although a method of blending a polymer component in the composition is also conceivable, there is a problem that the heat resistance, shape stability, and linear expansion coefficient of the cured product are deteriorated because the crosslinking density of the cured product is further reduced. is there.
In addition, in said patent document 1, it is not examined about the means which prevents the phenomenon in which a composition leaks from clearance, without using a special metal mold | die.

In general, since a lens controls a light path by combining materials having different refractive indexes, materials having various refractive indexes are desired. Since many of the materials disclosed in Patent Document 1 have a low refractive index, a variation of a high refractive index material that is excellent in heat resistance while maintaining excellent transparency is required.

The present invention has been made in view of the above problems, and is a molded article having excellent heat resistance and high refractive index while maintaining excellent optical performance such as transparency and shape stability due to thermal history. An object of the present invention is to provide a (meth) acrylate-based composition that has high workability because of its high viscosity, a resin obtained from the composition, and a molded body obtained by molding the resin. To do.

The present inventors have found that a (meth) acrylate-based composition containing a (meth) acrylate compound having a specific structure together with a (meth) acrylate compound having an adamantyl group can solve the above-mentioned problems. Was completed.

That is, the present invention provides the following [1] to [23].
[1] A (meth) acrylate compound (A) having an adamantyl group represented by the following general formula (A-1), and the following general formulas (bI) to (b-VII) in one molecule: A (meth) acrylate-based composition comprising a (meth) acrylate compound (B) having one or more of the following structures:

(In the formula (A-1), each R ¹ independently represents a hydrogen atom or a methyl group, and each X independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or 4 represents an oxyalkylene group, U represents an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group, or ═O formed by combining two U. k represents an integer of 0 to 15, m Represents an integer of 1 to 4.)

(In the above formulas (bI) to (b-VII), Y ^a represents a divalent organic group, and each R ⁶ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 and R ⁷ each independently represents a divalent organic group, p represents an integer of 0 to 4, q represents an integer of 0 to 3, and * represents a bonding portion. Show.)
[2] The (meth) acrylate composition according to [1], further including a (meth) acrylate compound (C) represented by the following general formula (C-1).

(In the above formula (C-1), each R ² independently represents a hydrogen atom or a methyl group, and Y ¹ represents a substituted or unsubstituted acyclic hydrocarbon group having 5 to 30 carbon atoms and —R From the group represented by '(OR') _L- (wherein R 'independently represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and L is an integer of 1 to 20). One or more acyclic organic groups selected, n represents an integer of 1 to 8)
[3] The component (B) is a (meth) acrylate compound (B1) having an isocyanurate structure represented by the general formula (bI) and a general formula (B-2) ) The (meth) acrylate composition according to [1] or [2] above, which contains one or more selected from acrylate compounds (B2).

(In the formula (B-2), each G independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms, and each R ⁴ independently represents Each represents a hydrogen atom or a methyl group, and each R ⁵ independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group, and a represents an integer of 2 to 8 And each b is independently a positive number from 1 to 4. Z represents the following general formulas (b-II-1) to (b-II-6) and the above general formula (b-III) ) To any one of the organic groups represented by (b-VII).)

(In the above general formulas (b-II-1) to (b-II-6), each R ⁶ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. And each R ⁷ independently represents a divalent organic group, p represents an integer of 0 to 4, q represents an integer of 0 to 3, and * represents a bonding portion.)
[4] The (meth) acrylate composition according to [3] above, wherein the component (B1) is a (meth) acrylate compound having an isocyanurate structure represented by the following general formula (B-1).

(In the formula (B-1), each R ³ independently represents a hydrogen atom or a methyl group, and D ¹ to D ³ each independently represents a divalent organic group.)
[5] Further, as component (D), a compound selected from a reaction compound (D1) of an epoxy compound and (meth) acrylic acid and a urethane (meth) acrylate compound (D2) other than the compound corresponding to component (B) The (meth) acrylate composition according to any one of the above [1] to [4], comprising at least a seed.
[6] The (meth) acrylate composition as described in [5] above, wherein the content of the component (D) is 2 to 50 parts by mass with respect to 100 parts by mass in total of the components (A) to (C) object.
[7] The component (B1) is included as the component (B), and the content of the component (B1) is 20 to 80% by mass based on the total amount of the components (A) to (C). [3] The (meth) acrylate composition according to any one of [6].
[8] The component (B1) and the component (B2) are included as the component (B), and the content of the component (B2) is 5 to 40% by mass with respect to the total amount of the components (A) to (C). The (meth) acrylate composition as described in [3] to [7] above.
[9] Any of the above [3] to [7], wherein the component (B1) is included as the component (B), and the viscosity of the (meth) acrylate composition at 25 ° C. is 1000 to 50000 mPa · s. (Meth) acrylate composition described in 1.
[10] The above (3), wherein the component (B2) is included as the component (B), and the content of the component (B2) is 30 to 85% by mass with respect to the total amount of the components (A) to (C). The (meth) acrylate composition according to any one of to [6].
[11] The above [3] to [6] and [[6], wherein (B2) component is included as component (B), and the viscosity of the (meth) acrylate composition at 25 ° C. is 500 to 50000 mPa · s. [10] The (meth) acrylate composition according to any one of [10].
[12] The above [1] or [2], wherein the component (B) includes a (meth) acrylate compound (B3) having a phenyl group represented by the following general formula (B-3a) or (B-3b) The (meth) acrylate composition described in 1.

(In the formulas (B-3a) and (B-3b), each X ¹ independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms; ^a represents a divalent organic group, R ²² and R ²³ each independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group, and R ^4a , R ^4b each independently represents a hydrogen atom or a methyl group, and R ⁶ to R ¹³ each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. A and b each represent an added mole number of alkylene oxide, each being a positive number, and an average value of a + b is 2 to 4. c represents an integer of 1 to 5, and d represents 1 to 5 Represents an integer, and e represents an integer of 1 to 5.)
[13] The organic group Y ^a in the general formula (B-3a) or (B-3b) is —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —, —CH ₂ The (meth) acrylate composition according to [12], which is any one of —, —O—, and —CO—.
[14] The (meth) acrylate group according to [12] or [13], further including a (meth) acrylate compound (B2 ′) represented by the following general formula (B-2a) as the component (B) Composition.

(In the formula (B-2a), Z represents a divalent organic group represented by the general formula (b-III), and R ¹⁴ and R ¹⁵ each independently represents an alkylene having 1 to 4 carbon atoms. R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a methyl group, and f and g represent the number of added moles of alkylene oxide, each being a positive number, and the average value of f + g is 2-4.)
[15] The mass ratio of the content of the component (B3) to the content of the component (B2 ′) [(B3) component / (B2 ′) component] is 15/85 to 40/60 above. ] (Meth) acrylate type | system | group composition as described in.
[16] The (meta) component according to any one of the above [12] to [15], wherein the content of the component (A) is 5 to 40% by mass with respect to the total amount of the components (A) to (C) ) Acrylate composition.
[17] The (meth) acrylate composition according to any one of [12] to [16] above, having a viscosity at 25 ° C. of 300 to 50,000 mPa · s.
[18] A resin obtained by polymerizing the (meth) acrylate composition according to any one of [1] to [17].
[19] A molded product obtained by molding the resin according to [18].
[20] The molded product according to [19], wherein the molded product has a total light transmittance of 85% or more.
[21] The molded article according to the above [19] or [20], wherein the molded article has a refractive index at d-line of 1.45 or more.
[22] The molded body according to any one of [19] to [21], wherein the molded body has an Abbe number of 60 or less at the d-line.
[23] The molded body according to any one of [19] to [22], wherein the molded body is an optical component.

The present invention is classified into three inventions (first to third inventions) depending on the component (B) used.
Examples of the first aspect of the present invention include the following [1a] to [13a].
[1a] A (meth) acrylate compound (B) including a (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1) and a (meth) acrylate compound (B1) having an isocyanurate structure And a (meth) acrylate-based composition comprising the (meth) acrylate compound (C) represented by the general formula (C-1).
[2a] The (meth) acrylate composition according to [1a] above, wherein the component (B1) is a (meth) acrylate compound having an isocyanurate structure represented by the general formula (B-1).
[3a] The (meth) acrylate composition according to [1a] or [2a], further including a (meth) acrylate compound (B2) represented by the above general formula (B-2) as the component (B) object.
[4a] The (meth) acrylate composition according to [3a] above, wherein the content of the component (B2) is 5 to 40% by mass with respect to the total amount of the components (A) to (C).
[5a] The content of the component (B1) according to any one of the above [1a] to [4a], wherein the content of the component (B1) is 20 to 80% by mass with respect to the total amount of the components (A) to (C). ) Acrylate composition.
[6a] Further, as the component (D), a compound selected from a reaction compound (C1) of an epoxy compound and (meth) acrylic acid and a urethane (meth) acrylate compound (D2) other than the compound corresponding to the component (B) The (meth) acrylate composition according to any one of the above [1a] to [5a], comprising at least seeds.
[7a] The (meth) acrylate composition as described in [6a] above, wherein the content of the component (D) is 2 to 50 parts by mass with respect to 100 parts by mass in total of the components (A) to (C) object.
[8a] The (meth) acrylate composition according to any one of the above [1a] to [7a], wherein the viscosity of the (meth) acrylate composition at 25 ° C. is 1000 to 50000 mPa · s.
[9a] A resin obtained by polymerizing the (meth) acrylate composition according to any one of [1a] to [8a].
[10a] A (meth) acrylate compound (B) including a (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1) and a (meth) acrylate compound (B1) having an isocyanurate structure ) And a (meth) acrylate-based composition containing the (meth) acrylate compound (C) represented by the general formula (C-1), and a molded product obtained by molding a resin obtained by polymerization.
[11a] The molded article according to [10a], wherein the molded article has a total light transmittance of 85% or more.
[12a] The molded product according to [10a] or [11a] above, wherein the molded product has a refractive index of 1.45 to 1.65 at the d-line.
[13a] The molded body according to any one of [10a] to [12a], wherein the molded body is an optical component.

Further, examples of the second aspect of the present invention include the following [1b] to [10b].
[1b] including a (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1) and a (meth) acrylate compound (B2) represented by the general formula (B-2) A (meth) acrylate-based composition comprising a (meth) acrylate compound (B) and a (meth) acrylate compound (C) represented by the general formula (C-1).
[2b] The (meth) acrylate composition according to [1b] above, wherein the content of the component (B) is 30 to 85% by mass with respect to the total amount of the components (A) to (C).
[3b] Further, as component (D), a compound selected from a reaction compound (D1) of an epoxy compound and (meth) acrylic acid and a urethane (meth) acrylate compound (D2) other than the compound corresponding to component (B) The (meth) acrylate composition according to the above [1b] or [2b], which contains seeds or more.
[4b] The (meth) acrylate composition according to [3b] above, wherein the content of the component (D) is 2 to 50 parts by mass with respect to 100 parts by mass in total of the components (A) to (C) object.
[5b] The (meth) acrylate composition according to any one of [1b] to [4b] above, wherein the viscosity of the (meth) acrylate composition at 25 ° C. is 500 to 50,000 mPa · s.
[6b] A resin obtained by polymerizing the (meth) acrylate composition according to any one of [1b] to [5b].
[7b] A molded product obtained by molding the resin according to [6b].
[8b] The molded product according to [7b], wherein the molded product has a total light transmittance of 85% or more.
[9b] The molded body according to [7b] or [8b] above, wherein the molded body has a refractive index of 1.45 to 1.65 at the d-line.
[10b] The molded body according to any one of [7b] to [9b], wherein the molded body is an optical component.

Furthermore, as the third aspect of the present invention, the following [1c] to [15c] can be mentioned.
[1c] A (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1) and a phenyl group represented by the general formula (B-3a) or (B-3b) The (meth) acrylate type composition containing the (meth) acrylate compound (B) containing the (meth) acrylate compound (B3).
[2c] The (meth) acrylate composition according to [1c] above, wherein one or more of R ⁶ to R ^{13 in} the general formula (B-3a) or (B-3b) is a bromine atom.
[3c] (1c) or (2c) above, wherein R ⁶ , R ⁸ , R ¹¹ , and R ^{13 in the} general formula (B-3a) or (B-3b) are t-butyl groups ( (Meth) acrylate-based composition.
[4c] The organic group Y ^a in the general formula (B-3a) or (B-3b) is —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —, —CH The (meth) acrylate composition according to any one of [1c] to [3c] above, which is any one of _2- , —O—, and —CO—.
[5c] As the component (B), a (meth) acrylate compound (B2 ′) represented by the above general formula (B-2a) and a (meth) acrylate compound represented by the above general formula (C-1) ( The (meth) acrylate composition according to any one of [1c] to [4c] above, which contains one or more selected from C).
[6c] The mass ratio of the content of the component (B3) to the content of the component (B2 ′) [component (B3) / component (B2 ′)] is 15/85 to 40/60, ] (Meth) acrylate type | system | group composition as described in.
[7c] The content of the component (A) in any one of the above [1c] to [6c], wherein the content of the component (A) is 5 to 40% by mass relative to the total amount of the components (A) to (C) ) Acrylate composition.
[8c] The above-mentioned [1c] to [7c], wherein the total content of the components (A) to (C) is 60 to 100% by mass with respect to the total amount of the (meth) acrylate compound contained in the composition. ] The (meth) acrylate type composition in any one of.
[9c] The (meth) acrylate composition according to any one of [1c] to [8c] above, having a viscosity at 25 ° C. of 300 to 50000 mPa · s.
[10c] A resin obtained by polymerizing the (meth) acrylate composition according to any one of [1c] to [9c].
[11c] A (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1) and a phenyl group represented by the general formula (B-3a) or (B-3b) The molded object formed by shape | molding resin obtained by superposing | polymerizing the (meth) acrylate type composition containing a (meth) acrylate compound (B3).
[12c] The molded article according to [11c] above, wherein the molded article has a refractive index at d-line of 1.55 or more.
[13c] The molded body according to [11c] or [12c] above, wherein the molded body has an Abbe number of 40 or less at the d-line.
[14c] The molded product according to any one of [11c] to [13c] above, wherein the molded product has a total light transmittance of 85% or more.
[15c] The molded body according to any one of [11c] to [14c], wherein the molded body is an optical component.

The (meth) acrylate composition of the present invention can be a molded article having excellent heat resistance and high refractive index while maintaining shape stability due to excellent optical performance such as transparency and thermal history, and high refractive index. Excellent workability due to viscosity.
Therefore, by using the above composition, it is possible to produce a molded body such as an optical component excellent in optical performance by improving productivity without using a special mold or the like.

In the following description, the (meth) acrylate compound is used to mean both an acrylate compound and a methacrylate compound (and other synonymous terms are also the same).
Moreover, in this invention, the molecular weight of each component means a number average molecular weight, and is the value computed from the polystyrene conversion measured with the following apparatus and conditions by the gel permeation chromatography (GPC) method.
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
・ Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
・ Flow rate: 1.0 ml / min ・ Sample concentration: 2.2 mg / ml
・ Injection volume: 160 μl
-Calibration curve: Universal Calibration
・ Analysis program: HT-GPC (Ver.1.0)

[(Meth) acrylate-based composition]
The (meth) acrylate-based composition of the present invention (hereinafter also simply referred to as “composition”) includes a (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1), and A (meth) acrylate compound (B) having one or more of the structures represented by the above general formulas (bI) to (b-VII) is included in the molecule.
Further, the composition of the present invention can further contain a (meth) acrylate compound (C) represented by the above general formula (C-1) as an optional component, and a molded body is produced from the composition. From the viewpoint of suppressing the occurrence of cracks, it is preferable to include the component (C).

From the viewpoint of increasing the viscosity of the resulting composition, the composition of the present invention is a reaction compound of an epoxy compound and (meth) acrylic acid other than the compound corresponding to the component (B) as the component (D) ( It is preferable that 1 or more types chosen from D1) and a urethane (meth) acrylate compound (D2) are included.
In addition, the composition of the present invention may contain other additives such as an antioxidant, a polymerization initiator, and a light stabilizer, if necessary.

The viscosity of the composition of the present invention at 25 ° C. is preferably 300 to 50000 mPa · s, more preferably 400 to 40000 mPa · s, still more preferably 450 to 20000 mPa · s.
In addition, the value of the viscosity in 25 degreeC of said composition means the value measured based on the method as described in an Example.

The composition of the present invention is classified into the following three compositions (first to third compositions) depending on the difference in the structure of the component (B) contained in the composition.
The first composition of the present invention contains a (meth) acrylate compound (B1) having an isocyanate structure represented by the above general formula (bI) as the component (B). By including the component (B1) in the composition, the viscosity of the composition can be increased, and the processability of the composition is improved.
The 2nd composition of this invention contains the (meth) acrylate compound (B2) represented by the said general formula (B-2) as (B) component. By including the component (B2) in the composition, it is possible to increase the viscosity of the resulting composition, improve the processability of the composition, and increase the refractive index of the molded product obtained from the composition.
The third composition of the present invention contains a (meth) acrylate compound having a phenyl group represented by the above general formula (B-3a) or (B-3b) as the component (B). By including (B3) component in a composition, the refractive index of the molded object obtained from this composition can be raised.
In addition, the composition of this invention may correspond to several types, such as the structure of (B) component to contain, and the case where it contains 2 or more types of (B) component.
First, each component contained in the composition of the present invention (the first to third compositions of the present invention) will be described.

[Component (A): (Meth) acrylate compound (A) having an adamantyl group represented by formula (A-1)]
The composition of the present invention contains a (meth) acrylate compound having an adamantyl group represented by the following general formula (A-1) as the component (A). The component (A) mainly becomes a hard segment when the composition of the present invention is polymerized to form a resin, and becomes a site having low mobility between molecules. Moreover, the heat resistance of the molded object obtained from this composition can be improved by containing (A) component.

In the above formula (A-1), each R ¹ independently represents a hydrogen atom or a methyl group.
Each X independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms.
Examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group.
Examples of the oxyalkylene group having 1 to 4 carbon atoms include an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group.
Among these X, a single bond is preferable from the viewpoint of improving the heat resistance of a molded product obtained from the composition.

In the above formula (A-1), 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. In addition, several U may be the same and may differ.
Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group and the like.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
K represents the number of substituents U in the adamantyl skeleton, and represents an integer of 0 to 15, preferably an integer of 0 to 10.

In the above formula (A-1), m represents an integer of 1 to 4, preferably an integer of 1 to 2.
In the general formula (A-1), examples of the compound in which m is 1 include adamantylmethanol (meth) acrylate and adamantylethanol (meth) acrylate.
Examples of the compound in which m is 2 include adamantyl dimethanol di (meth) acrylate and adamantyl diethanol di (meth) acrylate.
Examples of the compound in which m is 3 include adamantyltrimethanol tri (meth) acrylate and adamantyltriethanol tri (meth) acrylate.
Examples of the compound in which m is 4 include adamantyl tetramethanol tetra (meth) acrylate and adamantyl tetraethanol tetra (meth) acrylate.

These components (A) may be used alone or in combination of two or more.
The content of the component (A) in the composition of the present invention is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and further preferably 9 to 30% by mass with respect to the total amount of the composition. It is.

[Component (B): (Meth) acrylate compound (B) having one or more structures represented by general formulas (bI) to (b-VII) in one molecule]
The composition of the present invention comprises, as component (B), a (meth) acrylate compound (B) having one or more of the structures represented by the following general formulas (bI) to (b-VII) in one molecule including.

In the general formulas (bI) to (b-VII), Y ^a represents a divalent organic group, and R ⁶ each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number 1 to 6 alkoxy groups, and each R ⁷ is independently a divalent organic group. P represents an integer of 0 to 4, and q represents an integer of 0 to 3. * Represents a binding moiety.

Examples of the divalent organic group represented by Y ^a include —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —, —CH ₂ —, —O—, —CO— and the like. -C (CH ₃ ) ₂ -is preferred from the viewpoint of increasing the refractive index of the molded product obtained from the composition.

Examples of the halogen atom represented by R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, pentyl group, hexyl group and the like. It is done.
Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ⁶ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group and the like.

Examples of the divalent organic group represented by R ⁷ include divalent aliphatic groups such as linear or branched alkylene groups, oxyalkylene groups, alkylidene groups, alkenylene groups, phenylene groups, and biphenylene groups. And arylene groups such as a naphthylene group.
When R ⁷ is an alkylene group, an oxyalkylene group, an alkylidene group, or an alkenylene group, the number of carbon atoms in these groups is preferably 1-18, more preferably 1-12, still more preferably 1-6, and more. More preferably, it is 1 to 3.
When R ⁷ is an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12.

These components (B) may be used alone or in combination of two or more.
The content of the component (B) in the composition of the present invention is preferably 25 to 95% by mass, more preferably 30 to 92% by mass, and still more preferably 40 to 88% by mass with respect to the total amount of the composition. It is.

In the composition of the present invention, the component (B) preferably contains one or more kinds obtained from the above-mentioned component (B1), component (B2), and component (B3). The components (B1) to (B3) may be used alone or in combination of two or more.
From the viewpoint of increasing the refractive index of a molded article obtained from the composition while increasing the viscosity of the composition, a composition containing the component (B1) and the component (B2) is preferable as the component (B).
Further, from the viewpoint of obtaining a composition excellent in processability by further increasing the viscosity of the composition while further increasing the refractive index of the molded product obtained from the composition, as the component (B), the components (B3) and (B2 ) Component is preferred.
Details of the components (B1) to (B3) will be described below.

[(B1) component: (meth) acrylate compound (B1) having an isocyanurate structure]
The composition of the present invention preferably contains a (meth) acrylate compound (B1) having an isocyanurate structure represented by the above general formula (bI) as the component (B). By containing (B1) component in a composition, the viscosity of the said composition can be raised and the workability of a composition can be improved. Moreover, the optical characteristic of the molded object obtained from a composition also becomes favorable.

The component (B1) is preferably a (meth) acrylate compound having an isocyanurate structure represented by the following general formula (B-1) from the viewpoint of increasing the viscosity of the composition and improving the processability of the composition.

In the above formula (B-1), R ³ each independently represents a hydrogen atom or a methyl group, and D ¹ to D ³ each independently represents a divalent organic group.
Examples of the divalent organic group represented by D in the formula (B-1) include divalent aliphatic groups such as a linear or branched alkylene group, an oxyalkylene group, an alkylidene group, and an alkenylene group. And arylene groups such as a phenylene group, a biphenylene group, and a naphthylene group.
The number of carbon atoms in the alkylene group, oxyalkylene group, alkylidene group, and alkenylene group is preferably 1-18, more preferably 1-12, still more preferably 1-6, and still more preferably 1-3.
The number of carbon atoms of the arylene group is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12.
In the formula (B-1), examples of the divalent organic group represented by D also include a group represented by the following formula (B-1a).

In the above formula (B-1a), R ¹¹ and R ¹² each independently represents an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms. D represents an integer of 1 to 10, preferably an integer of 1 to 4. * Represents a binding moiety.

Among these divalent organic groups, from the viewpoint of increasing the viscosity of the composition, an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, and a group represented by the above formula (B-1a) Is preferred. These divalent organic groups D ¹ to D ³ may be all the same or different from each other.
These components (B1) may be used alone or in combination of two or more.

[Component (B2): (Meth) acrylate Compound (B2) Represented by Formula (B-2)]
The composition of the present invention preferably contains a (meth) acrylate compound (B) represented by the following general formula (B-2) as the component (B). By containing (B2) component in a composition, the refractive index of the molded object obtained from the said composition can be raised, raising the viscosity of the said composition and improving the workability of a composition.

In the above formula (B-2), each G independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms, and R ⁴ each independently represents hydrogen. R ⁵ represents an atom or a methyl group, and each R ⁵ independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group. a represents an integer of 2 to 8, and each b is independently a positive number of 1 to 4, preferably 1 to 3, more preferably 1 to 2. When R ⁵ is an alkylene group having 1 to 4 carbon atoms, the values of b each independently represent an average value of the number of added moles of alkylene oxide.
Examples of the alkylene group having 1 to 4 carbon atoms in G include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group. Examples of the oxyalkylene group 4 include an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group.
Examples of the alkylene group having 1 to 4 carbon atoms in R ⁵ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group.
Examples of the alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group include groups in which a hydrogen atom in the groups listed as the alkylene group having 1 to 4 carbon atoms is substituted with a hydroxy group. Groups represented by formulas (a) to (c) are preferred.

(In the above formulas (a) to (c), * represents a binding moiety.)

Z represents any one of organic groups represented by the following general formulas (b-II-1) to (b-II-6) and the general formulas (b-III) to (b-VII).

In the general formulas (b-II-1) to (b-II-6), each R ⁶ is independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Each R ⁷ independently represents a divalent organic group. P represents an integer of 0 to 4, and q represents an integer of 0 to 3.
Further, * represents a bonding part, but the organic groups represented by the above general formulas (b-II-1) to (b-II-6) are preferably bonded at the para position.
Examples of the alkyl group and alkoxy group represented by R ⁶ and the divalent organic group represented by R ⁷ include the groups exemplified for R ⁶ and R ⁷ in the general formulas (bI) to (b-VII). Can be mentioned.

Among these, from the viewpoint of improving the heat distortion resistance of a molded article obtained from the composition, Z in the general formula (B-2) is an organic group represented by the general formula (b-II-1). A (meth) acrylate compound is preferred.
Examples of the (meth) acrylate compound in which Z is an organic group represented by the general formula (b-II-1) include (meth) acrylic acid adducts of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl. Examples include (meth) acrylic acid adducts of ethers, and examples of commercially available products include epoxy esters 3002M, 3002A, 3000M, 3000MK, and 3000A (manufactured by Kyoeisha Chemical Co., Ltd.).
These components (B2) may be used alone or in combination of two or more.

[(B3) component: (meth) acrylate compound (B3) having a phenyl group represented by formula (B-3a) or (B-3b)]
The composition of the present invention preferably contains a (meth) acrylate compound having a phenyl group represented by the following general formula (B-3a) or (B-3b) as the component (B). By containing (B3) component in a composition, the refractive index of the molded object obtained from the said composition can be raised.

The formula (B-3a) and (B-3b) in, X ¹ is independently a single bond, an alkylene group, or an oxyalkylene group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, Y ^a Represents a divalent organic group, R ²² and R ²³ each independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group, R ^4a , R ^4b independently represents a hydrogen atom or a methyl group, and R ⁶ to R ¹³ each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms.

Examples of the alkylene group having 1 to 4 carbon atoms represented by X ¹ , R ²² , and R ²³ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group. Can be mentioned.
As the alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group represented by R ²² or R ²³ , a hydrogen atom in the above-mentioned groups listed as the alkylene group having 1 to 4 carbon atoms is substituted with a hydroxy group. A group is exemplified, but a group represented by the following formula is preferred.

(In the formula, * represents a binding moiety.)

R ⁶ to R ¹³ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms.
Examples of the halogen atom represented by R ⁶ to R ¹³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R ⁶ to R ¹³ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group , T-butyl, n-pentyl group and the like. From the viewpoint of increasing the refractive index of the molded article obtained from the composition, one or more of R ⁶ to R ¹³ are preferably bromine atoms, and R ⁶ , R ⁸ , R ¹¹ , and R ¹³ are t- A butyl group is preferred.

In the above formulas (B-3a) and (B-3b), Y represents a divalent organic group. For example, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ —, —CH ₂ —, —O—, —CO— and the like can be mentioned, and —C (CH ₃ ) ₂ — is preferable from the viewpoint of increasing the refractive index of a molded article obtained from the composition.

In the above formula (B-3a), a and b represent the number of added moles of alkylene oxide, each being a positive number, and the average value of a + b is 2 to 4.
In the above formula (B-3b), c represents an integer of 1 to 5, preferably 1 to 3. d represents an integer of 1 to 5, preferably 1 to 3. e represents an integer of 1 to 5, preferably 1 to 3. However, when X is a single bond, e represents an integer of 2 to 5, preferably 2 to 3.
In addition, you may use these (B3) components individually or in combination of 2 or more types.

In the composition of the present invention, the component (B3) and the component (B2) are preferably contained as the component (B), and together with the component (B3), the following general formula (B-2a) It is more preferable to contain the represented (meth) acrylate compound (B2 ′).
By including the component (B2 ′), the refractive index of the composition can be increased and a composition having a high viscosity can be obtained even if the content of the component (B3) is suppressed.
In addition, you may use the said (B2 ') component individually or in combination of 2 or more types.

In the above formula (B-2a), R ¹⁴ and R ¹⁵ each independently represents an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, Examples include butylene group and 2-methyltrimethylene group.
R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group.
f and g represent the number of added moles of alkylene oxide, each being a positive number, and the average value of f + g is 2-4.
Z represents a divalent organic group represented by the following general formula (b-III).

(In the above formula (b-III), R ⁶ , R ⁷ and p are as described above, and * represents a binding moiety.)

[Component (C): (Meth) acrylate Compound (C) Represented by Formula (C-1)]
The composition of the present invention contains a (meth) acrylate compound represented by the following general formula (C-1) as the component (C). (C) When the composition of the present invention is polymerized into a resin, the component (C) is mainly a soft segment, which is a site having many flexible sites, and the mobility of the polymer chain is increased in the molecule. It becomes a flexible part. Moreover, generation | occurrence | production of the crack at the time of obtaining a molded object from this composition can be suppressed by containing (C) component.

In the above formula (C-1), each R ² independently represents a hydrogen atom or a methyl group.
Y ¹ represents a substituted or unsubstituted acyclic hydrocarbon group having 5 to 30 carbon atoms and a group represented by —R ′ (OR ′) _L — (wherein R ′ is independently substituted Or an unsubstituted alkylene group having 1 to 4 carbon atoms, and L is an integer of 1 to 20).
In addition, as a substituent of the said acyclic hydrocarbon group and an alkylene group, a halogen atom, a hydroxyl group, an amino group etc. are mentioned, for example. Examples of the alkylene group having 1 to 4 carbon atoms represented by R ′ include the groups described above.
L is an integer of 1 to 20, preferably 2 to 15, and more preferably 2 to 10.
n represents an integer of 1 to 8, and is preferably an integer of 2 to 7, more preferably an integer of 3 to 6, from the viewpoint of improving the crosslinking density of the resin obtained from the composition of the present invention.

^{One selected} from a substituted or unsubstituted acyclic hydrocarbon group having 5 to 30 carbon atoms and a group represented by —R ′ (OR ′) _L — represented by Y ¹ in the above formula (C-1) The above acyclic organic group may have an ether bond, and may further include a linear hydrocarbon group having less than 5 carbon atoms, a branched hydrocarbon group, or the like.
The above group represented by Y ¹ is a site corresponding to the soft segment in the resin obtained from the composition, and the mobility of the polymer chain is increased in the molecule, which becomes a flexible site.

Here, when Y ¹ in the above formula (C-1) is a substituted or unsubstituted acyclic hydrocarbon group having 5 to 30 carbon atoms, the component (C) is represented by the following general formula (C— The (meth) acrylate compound (C1) represented by 1a) is preferred.

In the above formula (C-1a), R ² and n are the same as in the formula (C-1). Q ¹ is one or more organic groups selected from a linear hydrocarbon group having 1 to 30 carbon atoms and a branched hydrocarbon group having 3 to 30 carbon atoms, and these organic groups include an ether bond. It may be substituted with a halogen atom, a hydroxyl group, an amino group or the like.
Y ² is an acyclic hydrocarbon group having 5 to 30 carbon atoms, may contain an ether bond, and may be substituted with a halogen atom, a hydroxyl group, an amino group, or the like.

Examples of the linear hydrocarbon group having 1 to 30 carbon atoms in Q ¹ in the general formula (C-1a) include, for example, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-pentylene group. N-hexylene group, n-heptylene group, n-octylene group, 2-ethylhexylene group, n-nonylene group, n-decylene group, n-undecylene group, n-dodecylene group, n-tridecylene group, n- C1-C30 alkylene groups such as tetradecylene group, n-pentadecylene group, n-hexadecylene group, n-heptadecylene group, n-octadecylene group, and the like, and oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group Examples thereof include oxyalkylene groups having 1 to 30 carbon atoms such as

Examples of the branched hydrocarbon group having 3 to 30 carbon atoms in Q ¹ in the general formula (C-1a) include isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, and neopentyl group. Group, t-pentyl group, isohexyl group and the like.

The acyclic hydrocarbon group having 5 to 30 carbon atoms of Y ^{2 in} the general formula (C-1a) is represented by, for example, — (CH ₂ ) _r1 — or — (CH ₃ CH) _r1 —. An alkylene group (r1 is an integer of 5 to 30), a propylene group represented by — (CR ^c —CR ^d ) _r2 — (one of R ^c and R ^d is a hydrogen atom, the other is a methyl group, and r2 is 2 to 2) And an alkoxy group represented by — (CH ₂ O) _r3 — or — (CH ₃ CHO) _r3 — (wherein r3 is an integer of 5 to 30).
Among these, an alkylene group represented by — (CH ₂ ) _r1 — (r1 is an integer of 5 to 30), a propylene group represented by — (CR ^c —CR ^d ) _r2 — (R ^c , R ^d One is a hydrogen atom, the other is a methyl group, and r2 is preferably an integer of 2 to 15.

Of the (meth) acrylate compound (C1) represented by the general formula (C-1a), examples of the compound in which n is 2 include 1,5-pentanediol di (meth) acrylate and 1,6-hexane. Examples include diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,12-dodecanediol dimethacrylate, polybutadiene di (meth) acrylate, and hydrogenated polybutadiene di (meth) acrylate.

Among the (meth) acrylate compounds (C1) represented by the general formula (C-1a), examples of the compound having n of 3 or more include, for example, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, multifunctional Examples include polyester (meth) acrylate.

In addition, when Y ¹ in the above formula (C-1) is an acyclic organic group containing a group represented by —R ′ (OR ′) _L —, the component (C) is represented by the following general formula A (meth) acrylate compound (C2) represented by the formula (C-1b) is preferable.

In the above formula (C-1b), R ² and n are the same as in the formula (C-1), and Y ² is an acyclic carbon atom having 5 to 30 carbon atoms as in the formula (C-1a). It is a hydrogen group, may contain an ether bond, and may be substituted with a halogen atom, a hydroxyl group, an amino group or the like.
R ′ each independently represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. L is an integer of 1 to 20, preferably 2 to 15, more preferably 2 to 10.

Among the (meth) acrylate compounds (C2) represented by the general formula (C-1b), examples of the compound where n is 2 include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, L 2-20 polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, alkoxylated neopentyl glycol diacrylate, tetraethylene Examples include glycol di (meth) acrylate and alkoxylated cyclohexanediol diacrylate (manufactured by Sartomer Japan, Inc.).
Among these, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate having L of 2 to 20 are preferable.

In addition, among the (meth) acrylate compounds (C2) represented by the general formula (C-1b), examples of compounds in which n is 3 or more include, for example, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated triphenyl Methylolpropane tri (meth) acrylate, alkoxylated trimethylolpropane tri (meth) acrylate with L 2-20, 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 pentaerythris L 2-20 Tall tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, alkylated dipentaerythritol hexa (meth) acrylate, alkoxylated dipenta with L 2-20 Erythritol hexa (meth) acrylate, ethoxylated dipentaerythritol penta (meth) acrylate, propoxylated dipentaerythritol penta (meth) acrylate, alkylated dipentaerythritol hexa (meth) acrylate, alkoxylated dipentaerythritol with L of 2 or more Examples include penta (meth) acrylate and alkylated dipentaerythritol penta (meth) acrylate.

The number average molecular weight of the component (C) is preferably 140 to 50000, more preferably 250 to 40000, and still more preferably 350 to 10000, from the viewpoint of adjusting the viscosity of the composition and suppressing shape change after heat history. .

These components (C) may be used alone or in combination of two or more.
The content of the component (C) in the composition of the present invention is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and still more preferably 6 to 35% by mass with respect to the total amount of the composition. It is.

[Component (D): Reaction compound (D1) of epoxy compound and (meth) acrylic acid other than the compound corresponding to component (B), urethane (meth) acrylate compound (D2)]
The composition of the present invention further comprises, as component (D), a reaction compound (D1) of an epoxy compound and (meth) acrylic acid other than the compound corresponding to component (B) and a urethane (meth) acrylate compound (D2). It is preferable that 1 or more types chosen from are included.
In component (D1), due to the influence of hydrogen bonding between the oxygen atom of the carbonyl group and the hydrogen atom of the hydroxyl group formed by ring opening of the epoxy group of the epoxy compound, in component (D2), oxygen in the urethane bond Due to the influence of hydrogen bonding between atoms and hydrogen atoms, the viscosity of the composition containing these components can be increased.

The content of the component (D) (the total content of the components (D1) and (D2)) is preferably 2 to 50 parts by mass with respect to the total of 100 parts by mass of the components (A) to (C). The amount is more preferably 4 to 42 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 8 to 38 parts by mass, and still more preferably 9 to 25 parts by mass.
If the said content is 2 mass parts or more, the viscosity of a composition can fully be raised and the workability of a composition can be improved. On the other hand, if the said content is 50 mass parts or less, the viscosity of a composition will not become high too much and it can be set as the appropriate viscosity optimal for workability.

[(D1) component: a reaction compound (D1) of an epoxy compound and (meth) acrylic acid other than the compound corresponding to the component (B)]
The component (D1) is a compound other than the compound corresponding to the component (B), and is generated by the ring opening of the epoxy group of the epoxy compound and the reaction with (meth) acrylic acid.
Examples of the epoxy compound include alkyl glycidyl ether and allyl glycidyl ether.

Moreover, as an epoxy compound, the compound which has a 2 or more epoxy group is preferable.
As a reaction compound of an epoxy compound having two or more epoxy groups and (meth) acrylic acid, for example, a (meth) acrylic acid adduct of propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether ( (Meth) acrylic acid adduct, (meth) acrylic acid adduct of ethylene glycol diglycidyl ether, (meth) acrylic acid adduct of 1,4-butanediol diglycidyl ether, (1,5-pentanediol diglycidyl ether ( Of (meth) acrylic acid adduct, (meth) acrylic acid adduct of 1,6-hexanediol diglycidyl ether, (meth) acrylic acid adduct of 1,9-nonanediol diglycidyl ether, neopentyl glycol diglycidyl ether (Meth) acrylic acid adduct, glycerin di The glycidyl ether (meth) acrylic acid adduct and the like.

As a commercial item of (D1) component, epoxy ester 40EM, 70PA, 200PA, 80MFA (above, Kyoeisha Chemical Co., Ltd.) etc. are mentioned, for example.
In addition, you may use these (D1) components individually or in combination of 2 or more types.

[(D2) component: urethane (meth) acrylate compound (D2)]
The urethane (meth) acrylate compound (D2) is preferably a compound synthesized from a polyol component, an isocyanate component, and a hydroxy group-containing (meth) acrylate component. In addition, the number of functional groups of the component (D2) is preferably 2 or more, more preferably 2 to 4, and still more preferably, from the viewpoint of improving the high hardness, high elastic modulus, and heat distortion resistance of the molded product obtained from the composition. Is 2 to 3.

Examples of the bifunctional urethane (meth) acrylate compound include U-108A, UA-112P, UA-5201, UA-512, UA-412A, UA-4200, UA-4400, UA-340P, UA-2235PE, UA-160TM, UA-122P, UA-512, UA-W2, UA-7000, UA-7100 (above, trade name, manufactured by Shin-Nakamura Chemical Industry); CN962, CN963, CN964, CN965, CN980, CN981, CN982, CN983, CN996, CN9001, CN9002, CN9788, CN9873, CN978, CN9782, CN9783 (trade names, manufactured by Sartomer Japan, Inc.); M-1100, M-1200, M-1210, M-1310, M- 1600 (above, product name, UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1255, UN-6060PTM, UN-6060P, SH-500B (above, trade name, manufactured by Negami Kogyo); AH -600, AT-600 (above, trade name, manufactured by Kyoeisha Chemical Co., Ltd.); .

As trifunctional urethane (meth) acrylate compounds, for example, CN929, CN944B85, CN989, CN9008 (above, trade name, manufactured by Sartomer Japan, Inc.); EVERCRYL 294 / 25HD, EVERCRYL 4820 (trade name, manufactured by Daicel-Cytec);

Examples of the tetrafunctional or higher functional urethane (meth) acrylate compound include U-6HA, U-6H, U-15HA, UA-32P, U-324A, UA-7200 (above, trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) CN968, CN9006, CN9010 (above, trade name, manufactured by Sartomer Japan, Inc.); UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905, UN -952 (trade name, manufactured by Negami Kogyo Co., Ltd.);
These components (D2) may be used alone or in combination of two or more.

[Other ingredients]
The composition of the present invention may contain a (meth) acrylate compound that does not fall under the components (A) to (D) as long as the effects of the present invention are not impaired.
However, the total content of the components (A) to (D) is preferably 60 to 100% by mass, more preferably 75 to 100%, based on the total amount of the (meth) acrylate compound contained in the composition of the present invention. % By mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.

Moreover, you may mix | blend antioxidant and a polymerization initiator as needed.
(Antioxidant)
The composition of this invention can contain antioxidant as needed.
Examples of antioxidants include hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, thioether antioxidants, vitamin antioxidants, lactone antioxidants, and amine antioxidants. Etc.
Among these antioxidants, hindered phenol antioxidants are preferable from the viewpoint of heat resistance and yellowing resistance.
The number average molecular weight of the antioxidant is preferably 300 to 1500, and more preferably 330 to 1300, from the viewpoints of heat resistance and yellowing resistance.

Examples of the hindered phenol antioxidant include Irganox 1010, 1076, 1330, 3114, 3125 (all are trade names, manufactured by BASF), Adekastab AO-20, AO-50, AO-50 -60, AO-80, AO-30, AO-40 (all are trade names, manufactured by ADEKA Corporation), BHT (trade names, manufactured by Takeda Pharmaceutical Co., Ltd.), Cyanox 1790 (trade names, And commercially available products such as Sumilizer GP, GM, GS, and GA-80 (all are trade names, manufactured by Sumitomo Chemical Co., Ltd.).

Examples of phosphorus antioxidants include IRAGAFOS 168, 12, 38, P-EPQ, 126 (all are trade names, manufactured by BASF), ADKSTAB329K, PEP-36, PEP-8, Commercial products such as HP-10, 2112, 260, 522A (all are trade names, manufactured by ADEKA Corporation), Weston 618, 619G, 624 (all are trade names, manufactured by GE) Is mentioned.

Examples of sulfur-based antioxidants include DSTP “Yoshitomi”, DLTP “Yoshitomi”, DLTOIB, DMTP “Yoshitomi” (all of which are trade names, manufactured by Yoshitomi Co., Ltd.), Seenox 412S (trade name, Sipro Kasei Co., Ltd. ), Cyanox 1212 (trade name, manufactured by Cyanamid Co., Ltd.), TP-D, TPS, TPM, TPL-R (all of which are trade names, manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the thioether-based antioxidant include commercially available products such as ADK STAB AO-412S and AO-503 (all of which are trade names, manufactured by ADEKA Corporation).

Examples of vitamin antioxidants include commercially available products such as tocopherol (trade name, manufactured by Eisai Co., Ltd.) and Irganox E201 (trade name, manufactured by BASF).

Examples of the lactone antioxidant include commercially available products such as compounds described in JP-A-7-233160 and JP-A-7-247278, and HP-136 (trade name, manufactured by BASF). .

Examples of the amine-based antioxidant include commercially available products such as Irgastab FS042 (trade name, manufactured by BASF) and GENOX EP (trade name, manufactured by Crompton).

These antioxidants can be used alone or in combination of two or more.
The blending amount of the antioxidant is preferably based on 100 parts by mass of the total of the components (A) to (C) from the viewpoint of improving the transparency of the molded product obtained from the composition and suppressing yellowing. Is 0.1 to 20 parts by mass, more preferably 1 to 18 parts by mass, and still more preferably 1.5 to 15 parts by mass.

(Polymerization initiator)
The composition of this invention can mix | blend a polymerization initiator as needed.
As the polymerization initiator, any one of a thermal polymerization initiator that is cleaved by heat to generate an initiation radical, and a photopolymerization initiator that generates an initiation radical by irradiation with active energy rays such as light, electron beam, and radiation can be used. it can.
When a thermal polymerization initiator is used, the polymerization reaction can be promoted by heating the composition containing the thermal polymerization initiator at 40 to 200 ° C. On the other hand, when a photopolymerization initiator is used, the composition containing the photopolymerization initiator is irradiated with ultraviolet rays or the like with a cumulative amount of light of 50 to 2000 mJ / cm ² using a mercury xenon lamp or the like as a light source, It can be polymerized.

Examples of the thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1,3,3-tetramethylbutyl Hydroperoxides such as hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide, benzoyl peroxide, and Diacyl peroxides such as m-toluylbenzoyl peroxide; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide Xyl) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) ) Dialkyl peroxides such as hexene; 1,1-di (t-butylperoxy-3,5,5-trimethyl) cyclohexane, 1,1-di-t-butylperoxycyclohexane, and 2,2-di (t Peroxyketals such as -butylperoxy) butane; 1,1,3,3-tetramethylbutylperoxyneodicarbonate, α-cumylperoxyneodicarbonate, t-butylperoxyneodicarbonate, t-hexylperoxypivalate, t -Butylperoxypivalate, 1,1,3,3-tetramethylbuty Ruperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate 1,1,3,3-tetramethylbutylperoxy-3,5,5-trimethylhexanate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5 Alkyl peroxyesters such as trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and dibutylperoxytrimethyladipate; di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, Bi (1,1-butylcyclohexaoxydicarbonate), diisopropyloxydicarbonate, t-amylperoxyisopropylcarbonate, t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexylcarbonate, and 1,6-bis (t -Peroxycarbonates such as -butylperoxycarboxy) hexane; 1,1-di (t-hexylperoxy) cyclohexane, (4-t-butylcyclohexyl) peroxydicarbonate and the like. Among these, diacyl peroxides, peroxyketals, alkyl peroxy esters, and 1,1-di (t-hexylperoxy) cyclohexane are preferable. Lauroyl peroxide and 1,1-di-t-butylperoxycyclohexane are preferable. T-butylperoxy-2-ethylhexanoate and 1,1-di (t-hexylperoxy) cyclohexane are more preferred.

Examples of the photopolymerization initiator include benzoin ether, 2,2-dimethoxy-1,2-diphenylethane-1-one (commercially available product: “IRGACURE651 (trade name) manufactured by BASF)”, 1-hydroxy-cyclohexyl. -Phenyl-ketone (commercial product: “IRGACURE184 (trade name) manufactured by BASF)”, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (commercial product: “DAROCUR 1173 (commercial product, product of BASF) Name) ”), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (commercially available product:“ IRGACURE2959 (trade name, manufactured by BASF) ”) ), 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] pheny ] -2-Methyl-propan-1-one (commercially available product: “IRGACURE127 (trade name) manufactured by BASF”)), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Commercially available product: “IRGACURE907 (manufactured by BASF, trade name)”), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (commercially available product: “IRGACURE369 (manufactured by BASF, Product name) ”), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-monophorinyl) phenyl] -1-butanone (commercially available product:“ IRGACURE 379 (BASF) Product name) ”), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available product:“ DAROCUR TPO ” BASF, trade name))), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercial product: “IRGACURE819 (trade name), produced by BASF”)), bis (η5-2,4- Cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (commercially available product: “IRGACURE784 (trade name, manufactured by BASF)”), 1, 2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (commercial product: “IRGACURE OXE 01 (trade name, manufactured by BASF)”), Etanone-1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (commercial product: “IRGACURE O E 02 (BASF Co., Ltd., trade name), and the "), and the like.

These polymerization initiators can be used alone or in combination of two or more.
The blending amount of the polymerization initiator is preferably 0.01 to 12 parts by mass, more preferably 0 with respect to 100 parts by mass in total of the components (A) to (C), from the viewpoint of effectively promoting the polymerization reaction. 1-8 parts by mass, more preferably 0.3-5 parts by mass.

(Other additives)
The composition of the present invention includes a light stabilizer, an ultraviolet absorber, a lubricant, a plasticizer, an antistatic agent, an inorganic filler, a colorant, an antistatic agent, a release agent, as long as the effects of the present invention are not impaired. You may mix | blend additives, such as a flame retardant. Further, for the purpose of improving the adhesion with inorganic compounds such as titanium oxide and silicon oxide, additives such as a silane coupling agent containing a methacryloxy group or an acryloxy group of the silane compound may be blended.

[Contents of components (A) to (C) in the first composition of the present invention and the viscosity of the composition]
The content of the component (A) in the first composition of the present invention is based on the total amount of the components (A) to (C) from the viewpoint of improving the heat resistance of the molded product obtained from the composition. The amount is preferably 5 to 60% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 35% by mass.
In the present invention, the total amount of the components (A) to (C) does not exceed 100% by mass (the same applies hereinafter).

The content of the component (B1) in the first composition of the present invention is (A) from the viewpoint of appropriately increasing the viscosity of the composition and suppressing the influence by hydrolysis under high temperature and high humidity. It is preferably 20 to 80% by mass, more preferably 25 to 77% by mass, and still more preferably 30 to 75% by mass with respect to the total amount of the component (C).
If the said content is 20 mass% or more, the viscosity of the composition obtained can be raised moderately and the workability of a composition can be improved.
On the other hand, if the said content is 80 mass% or less, the phenomenon that (C) component itself hydrolyzes under high temperature and high humidity and the molded object which consists of this composition discolors can be suppressed.

Here, as the component (B), the content of the component (B1) when the component (B2) is not contained is more preferably 40 to 77 mass with respect to the total amount of the components (A) to (C). %, More preferably 50 to 75% by mass.
In addition, when the component (B2) is contained as the component (B), the content of the component (B1) is more preferably 25 to 70% by mass with respect to the total amount of the components (A) to (C). More preferably, it is 30 to 60% by mass, and still more preferably 35 to 55% by mass.

In the 1st composition of this invention, as (B) component, when using together (B1) component and (B2) component, as content of (B2) component, improving the viscosity of a composition, From the viewpoint of increasing the refractive index of the molded product obtained from the composition, it is preferably 5 to 40% by mass, more preferably 7 to 30% by mass, and still more preferably based on the total amount of the components (A) to (C). 10 to 25% by mass.
If the said content is 30 mass% or more, it can improve a viscosity and can be set as the composition excellent in workability. On the other hand, if the said content is 85 mass% or less, the viscosity of a composition will not rise too much and the moldability of the composition obtained can be made favorable.

In the first composition of the present invention, when the component (B1) and the component (B2) are used in combination as the component (B), the mass ratio of the content of the component (B1) and the content of the component (B2) [(B1) component / (B2) component] is preferably 40/60 to 95/5, more preferably from the viewpoint of increasing the refractive index of the molded article obtained from the composition while improving the viscosity of the composition. Is 55/45 to 90/10, more preferably 60/40 to 85/15, and still more preferably 65/35 to 80/20.

The content of the component (C) in the first composition of the present invention is based on the total amount of the components (A) to (C) from the viewpoint of suppressing deformation and discoloration of the molded product obtained from the composition against heat. The content is preferably 0 to 50% by mass, more preferably 3 to 50% by mass, still more preferably 5 to 40% by mass, and still more preferably 7 to 30% by mass.

The viscosity at 25 ° C. of the first composition of the present invention is preferably 1000 to 50000 mPa · s, more preferably 1100 to 40000 mPa · s, still more preferably 1200 to 5000 mPa · s, and still more preferably, from the viewpoint of processability. Is 1400-3500 mPa · s.
In addition, the value of the viscosity in 25 degreeC of said composition is a value measured based on the method as described in an Example.

[Contents of components (A) to (C) in the second composition of the present invention and the viscosity of the composition]
The content of the component (A) in the second composition of the present invention is from the viewpoint of improving the heat resistance of the molded product obtained from the composition, with respect to the total amount of the components (A) to (C), The amount is preferably 5 to 60% by mass, more preferably 8 to 45% by mass, and still more preferably 12 to 30% by mass.

The content of the component (B2) in the second composition of the present invention is (A) to (C) from the viewpoint of increasing the refractive index of the molded product obtained from the composition while improving the viscosity of the composition. ) It is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, and still more preferably 45 to 70% by mass, based on the total amount of components.
If the said content is 30 mass% or more, it can improve a viscosity and can be set as the composition excellent in workability. On the other hand, if the said content is 85 mass% or less, the viscosity of a composition will not rise too much and the moldability of the composition obtained can be made favorable.

The content of the component (C) in the second composition of the present invention is from the viewpoint of suppressing deformation and discoloration of the molded product obtained from the composition with respect to the total amount of the components (A) to (C). The content is preferably 0 to 50% by mass, more preferably 5 to 50% by mass, still more preferably 10 to 45% by mass, and still more preferably 18 to 40% by mass.

The viscosity of the second composition of the present invention at 25 ° C. is preferably 500 to 50000 mPa · s, more preferably 700 to 40000 mPa · s, still more preferably 800 to 5000 mPa · s, and still more preferably, from the viewpoint of processability. Is 1000 to 2000 mPa · s.

[Contents of components (A) to (C) in the third composition of the present invention and the viscosity of the composition]
The content of the component (A) in the third composition of the present invention is preferably relative to the total amount of the components (A) to (C) from the viewpoint of improving the heat resistance of the molded product obtained from the composition. Is 5 to 40% by mass, more preferably 10 to 35% by mass, and still more preferably 15 to 30% by mass.

The content of the component (B3) in the composition of the present invention is preferably 10 to 95 with respect to the total amount of the components (A) to (C) from the viewpoint of increasing the refractive index of the molded article obtained from the composition. The mass is more preferably 15 to 90 mass%, still more preferably 20 to 85 mass%.
Here, the content of the component (B3) when the component (B2 ′) and the component (C) are not contained is preferably 60 to 95% by mass with respect to the total amount of the components (A) to (C). Preferably it is 65 to 90% by mass, more preferably 70 to 85% by mass.
The content of the component (B3) when containing at least one of the component (B2 ′) and the component (C) is preferably 10 to 80 relative to the total amount of the components (A) to (C). The mass is more preferably 15 to 75 mass%, still more preferably 20 to 70 mass%.

As described above, the third composition of the present invention includes the component (B2 ′) together with the component (B3), thereby increasing the refractive index of the composition even when the content of the component (B3) is suppressed. it can.
The content of the component (B2 ′) is preferably 10 to 85% by mass, more preferably 30 to 80% by mass, still more preferably 50 to 70% by mass, based on the total amount of the components (A) to (C) is there.
The mass ratio of the content of the component (B3) to the content of the component (B2 ′) [(B3) component / (B2 ′) component] is preferably 15/85 to 40/60, more preferably 20 / 80 to 35/65, more preferably 25/75 to 30/70.

As above-mentioned, the 3rd composition of this invention can suppress generation | occurrence | production of the crack at the time of obtaining a molded object from a composition by containing (C) component.
The content of the component (C) in the third composition of the present invention is appropriately determined within a range that does not impair the effect of the present invention to achieve a high refractive index, but the total amount of the components (A) to (C) The content is preferably 0 to 50% by mass, more preferably 5 to 45% by mass, and still more preferably 10 to 40% by mass.
The mass ratio of the content of the component (B) and the content of the component (C) [(B) component / (C) component] is preferably 100/0 to 60/40, more preferably 85/15. To 65/35, more preferably 90/10 to 70/30.

The viscosity at 25 ° C. of the third composition of the present invention is preferably 300 to 50000 mPa · s, more preferably 400 to 40000 mPa · s, and further preferably 450 to 20000 mPa · s from the viewpoint of moldability.

[Resin, molded body]
The resin of the present invention can be obtained by polymerizing the above-described composition of the present invention.
In polymerizing the composition, it is preferable to include the above-described polymerization initiator in the composition from the viewpoint of efficiency of the polymerization reaction.
Moreover, the molded object of this invention is a molded object formed by shape | molding the said resin.
As the polymerization and molding method, the same method as that for molding a normal thermosetting resin can be used. Examples thereof include a method of proceeding simultaneously with the polymerization and molding steps in injection molding, compression molding, transfer molding, insert molding, and the like of the liquid composition. Moreover, a molded object can also be obtained by a potting process, a coating process, etc., and a molded object can also be obtained by the method similar to shaping | molding of photocuring resin, such as UV hardening molding.

Since the composition of the present invention has high viscosity while maintaining optical performance, it is suitable for producing a molded body using a liquid resin molding method.
Liquid resin molding methods include liquid resin injection molding in which a liquid raw material composition or its prepolymer is injected into a high-temperature mold and cured by heating, and the 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.

Each optical performance and physical property of the molded article of the present invention produced as described above will be described.
The total light transmittance of the molded article of the present invention is preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more.

The amount of decrease in light transmittance (absolute value of the light transmittance) at a wavelength of 440 nm between the molded body after thermal history left at 260 ° C. for 10 minutes and the molded body before thermal history is preferably 5. It is 0% or less, more preferably 3.0% or less, and still more preferably 2.5% or less.
In addition, about the molded object obtained from the 1st composition of this invention, the reduction | decrease amount of the light transmittance in wavelength 440nm of the molded object after the heat history left to stand at 260 degreeC for 10 minute (s), and the molded object before a heat history. The absolute value of the difference in light transmittance is preferably 5.0% or less, more preferably 4.0% or less, and still more preferably 3.0% or less.
Moreover, about the molded object obtained from the 2nd composition of this invention, the reduction | decrease amount of the light transmittance in wavelength 440nm of the molded object after a heat history left to stand at 260 degreeC for 10 minute (s), and the molded object before a heat history. The absolute value of the difference in light transmittance is preferably 5.0% or less, more preferably 3.0% or less, and still more preferably 1.5% or less.
And about the molded object obtained from the 3rd composition of this invention, the reduction amount of the light transmittance in wavelength 440nm of the molded object after the heat history left to stand at 260 degreeC for 10 minute (s), and the molded object before a heat history. The absolute value of the difference in the light transmittance is preferably 0.5% or less, more preferably 0.4% or less, and still more preferably 0.35% or less.

The refractive index of the molded product of the present invention at the d-line (wavelength 589.3 nm) is preferably 1.45 or more, more preferably 1.50 or more, and further preferably 1.53 or more.
The refractive index at the d-line (wavelength: 589.3 nm) of the molded product obtained from the first composition of the present invention is preferably 1.45 to 1.65, more preferably 1.47 to 1. 60, more preferably 1.50 to 1.56.
Further, the refractive index of the molded product obtained from the second composition of the present invention at the d-line (wavelength: 589.3 nm) is preferably 1.45 to 1.65, more preferably 1.50 to 1. 63, and more preferably 1.53 to 1.60.
The refractive index of the molded product of the present invention obtained from the third composition of the present invention at the d-line (wavelength 589.3 nm) is preferably 1.55 or more, more preferably 1.55 to 1. 65, more preferably 1.55 to 1.60.

The Abbe number at the d-line (wavelength 589.3 nm) of the molded product of the present invention is preferably 60 or less, more preferably 55 or less, and still more preferably 50 or less.
The Abbe number at the d-line (wavelength 589.3 nm) of the molded product obtained from the first composition of the present invention is preferably 30 to 60, more preferably 35 to 52, and still more preferably 40 to 48. It is.
Further, the Abbe number of the molded product obtained from the second composition of the present invention at the d-line (wavelength: 589.3 nm) is preferably 30 to 60, more preferably 33 to 52, still more preferably 36 to 45. It is.
The Abbe number at the d-line (wavelength: 589.3 nm) of the molded product obtained from the third composition of the present invention is preferably 40 or less, more preferably 25 to 40, still more preferably 30 to 40, More preferably, it is 35-40.

The linear expansion coefficient of the molded product of the present invention is preferably 110 ppm or less, more preferably 90 ppm or less, and still more preferably 80 ppm or less.
The flexural modulus of the molded article of the present invention is preferably 2.0 GPa or more, more preferably 2.4 GPa or more, and still more preferably 2.8 GPa or more.
The bending strength of the molded article of the present invention is preferably 50 MPa or more, more preferably 60 MPa or more, and further preferably 70 MPa or more.
The Shore D hardness of the molded article of the present invention is preferably 60 or higher, more preferably 70 or higher, and still more preferably 77 or higher.
In particular, when the molded article of the present invention is an optical component, a certain degree of mechanical strength is required so as not to be deformed during manufacturing.
In addition, the value of each said physical property of a molded object means the value measured by the method as described in an Example.

As described above, since the molded article of the present invention is excellent in various optical performances, it is suitable as an optical component such as a lens used for various devices or a lens for optical communication.

Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
In addition, about each physical property of the composition obtained by the following Example and comparative example, and a molded object, it measured and evaluated based on the following method.

(1) Viscosity The viscosity of the obtained composition at 25 ° C. was measured using a viscometer (manufactured by Brooksfield, product name “LVDV-I +”) based on JIS K7117-1.
(2) Total light transmittance As a test piece, using the obtained molded body having a thickness of 3 mm, based on JIS K7105, using a haze meter (product name “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd.) The total light transmittance was measured.
(3) Amount of decrease in light transmittance at a wavelength of 440 nm after thermal history As a test piece, a spectrophotometer (product name “U-4100 Spectrometer, manufactured by Hitachi High-Tech Fielding Co., Ltd.) was used. The light transmittance at a wavelength of 440 nm was measured with a meter ").
Next, the test piece was placed on a stainless steel plate having a thickness of 1 mm and left at 260 ° C. for 10 minutes (hereinafter, this operation is also referred to as “thermal history 1”). For the test piece after heat history 1, the light transmittance at a wavelength of 440 nm was measured in the same manner as described above, and the amount of decrease in light transmittance at a wavelength of 440 nm before and after heat history 1 (absolute value of the difference in light transmittance). (%) Was calculated.
(4) Refractive index, Abbe number As a test piece, a d-line at 20 ° C. was used for a molded article obtained with a thickness of 3 mm using a refractometer (manufactured by Metricon, product name “Model 2010 Prism Coupler”). The refractive index and Abbe number at a wavelength of 589.3 nm were measured.
(5) Linear Expansion Coefficient The obtained molded product was 20 to 90 by a compression method with a load of 49 mN using a linear expansion measuring device (product name “TMA / SS6100” manufactured by Seiko Instruments Inc.) based on ASTM E831. The linear expansion coefficient in the temperature range of ° C. was measured and the linear expansion coefficient was calculated.
(6) Shape stability evaluation Using a plate-like molded body of 25 mm long × 25 mm wide × 2 mm thick, the three plate-like bodies were placed on a stainless steel plate having a thickness of 3 mm and left at 260 ° C. for 10 minutes. After (Heat History 1), the degree of deformation of the edge of the plate-like molded body was visually confirmed and evaluated according to the following criteria.
A: The edge portion is the same as before the heat history, and the shape stability is excellent.
F: The edge portion is uniformly rounded and inferior in shape stability.
(7) Flexural modulus, flexural strength About the obtained molded body, based on JIS K 6911, using a testing machine (product name “INSTRON 5567” manufactured by Instron Japan Company Limited), the flexural modulus (unit: : GPa) and bending strength (unit: MPa) were measured.
(8) Shore D hardness The Shore D hardness of the obtained molded product was measured based on JIS-K 6253 using a tester (manufactured by Kobunshi Keiki Co., Ltd., product name “ASKER P1”).

[Examples 1a to 8a, 1b to 8b, 1c to 5c, Comparative Examples 1a to 2a, 1b to 2b, 1c to 2c]
The components shown in Tables 1 to 3 were added in the blending amounts (solid content ratios) shown in Tables 1 to 3 and mixed to obtain compositions.
And when producing a molded object from this composition, between two stainless steel plates (length 70mm x width 70mm x thickness 3mm), two sheets of mirror-finished aluminum plates (length 70mm x width 70mm x A container obtained by sandwiching a Teflon (registered trademark) spacer (length 70 mm × width 70 mm × thickness 3 mm) between the sheets was used. The Teflon (registered trademark) spacer portion of the container is provided with a window of 30 mm length × 30 mm width × 3 mm thickness, and the composition can be poured into the container from the window.
The composition is poured from the window of the container, and the container is held so as not to leak. After performing polymerization and molding, a plate-like molded body was obtained by cooling to room temperature.

About the obtained composition and molded object, various physical-property values were measured with the above-mentioned method. The results are shown in Tables 1 to 3.
The components contained in the compositions of Examples and Comparative Examples shown in Tables 1 to 3 are as follows.

<(A) component>
“AM”: 1-adamantyl methacrylate (produced by Osaka Organic Chemical Industry Co., Ltd.) represented by the following formula (a1).

<(B) component>
“9300-1CL”: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the following formula (b1).

“BPE-80N”: ethoxylated bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the following formula (b2).

"Epoxy ester 3000MK": Bisphenol A diglycidyl ether methacrylic acid adduct represented by the following formula (b3) (manufactured by Kyoeisha Chemical Co., Ltd.).

"Epoxy ester 3000A": Bisphenol A diglycidyl ether acrylic acid adduct represented by the following formula (b4) (manufactured by Kyoeisha Chemical Co., Ltd.).

“SR-349”: ethoxylated bisphenol A type diacrylate (manufactured by Sartomer Japan, Inc.) represented by the following formula (b5).

“A-BPEF”: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene represented by the following formula (b6) (manufactured by Shin-Nakamura Chemical Co., Ltd.).

<(C) component>
“SR-399”: Dipentaerythritol pentaacrylate represented by the following formula (c1) (manufactured by Sartomer Japan KK, number average molecular weight 525).

“SR-499”: ethoxylated (6) trimethylolpropane triclarate represented by the following formula (c2) (manufactured by Sartomer Japan, Inc., number average molecular weight 560).

“SR-295”: Pentaerythritol tetraacrylate represented by the following formula (c3) (manufactured by Sartomer Japan KK, number average molecular weight 352).

<(D) component>
“CN929”: trifunctional urethane acrylate (manufactured by Sartomer Japan, Inc.).

<Other ingredients>
“A-DCP”: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the following formula (e).

“Thermal polymerization initiator”: 1,1-di (t-hexylperoxy) cyclohexane (manufactured by NOF Corporation) represented by the following formula (f1).

"Antioxidant (TP-D)": a thioether-based antioxidant represented by the following formula (f2) (manufactured by Sumitomo Chemical Co., Ltd., pentaerythrityltetrakis (3-laurylthiopropionate), number average molecular weight : 1162).
_{_{_{(H 25 C 12 SCH 2 CH}}} 2 COOCH 2) 4 C (f2)

“Antioxidant (ADK STAB A-80)”: a hindered phenol-based antioxidant represented by the following formula (f3) (manufactured by ADEKA Corporation, number average molecular weight: 741).

From Table 1, the compositions of Examples 1a to 8a all have high viscosities at 25 ° C. of 1000 mPa · s or more, and are excellent in workability. Further, the various optical performances of the molded products obtained from the compositions of Examples 1a to 8a were all good.
On the other hand, the compositions of Comparative Examples 1a and 2a both had low viscosities at 25 ° C., resulting in problems in workability.

From Table 2, the compositions of Examples 1b to 8b all have a high viscosity at 25 ° C. of 500 mPa · s or more, and are excellent in workability. Further, the various optical performances of the molded products obtained from the compositions of Examples 1b to 8b were all good.
On the other hand, the compositions of Comparative Examples 1b and 2b both had low viscosities at 25 ° C., resulting in problems with workability.

From Table 3, the molded products obtained from the compositions of Examples 1c to 5c all have a high refractive index of 1.55 or more at d-line (wavelength: 589.3 nm) at 20 ° C. Moreover, it can be seen that the light transmittance at 440 nm is high and the transparency is excellent. It can also be seen that the transparency does not decrease even after a heat history of 260 ° C., has very high heat resistance that can withstand the solder reflow process, and is excellent in shape stability.

The (meth) acrylate composition of the present invention has excellent processability due to its high viscosity, and also has excellent heat resistance while maintaining optical performance such as excellent transparency and shape stability due to thermal history. In addition, a molded article having a high refractive index can be obtained. Therefore, the (meth) acrylate composition of the present invention is suitable as a material for forming optical parts such as lenses used in various devices and lenses for optical communication.

Claims

The (meth) acrylate compound (A) having an adamantyl group represented by the following general formula (A-1), and the structure represented by the following general formulas (bI) to (b-VII) in one molecule A (meth) acrylate composition comprising a (meth) acrylate compound (B) having one or more.

(In the formula (A-1), each R 1 independently represents a hydrogen atom or a methyl group, and each X independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or 4 represents an oxyalkylene group, U represents an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group, or ═O formed by combining two U. k represents an integer of 0 to 15, m Represents an integer of 1 to 4.)

(In the above formulas (bI) to (b-VII), Y a represents a divalent organic group, and each R 6 independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 and R 7 each independently represents a divalent organic group, p represents an integer of 0 to 4, q represents an integer of 0 to 3, and * represents a bonding portion. Show.)
The (meth) acrylate composition according to claim 1, further comprising a (meth) acrylate compound (C) represented by the following general formula (C-1).

(In the above formula (C-1), each R 2 independently represents a hydrogen atom or a methyl group, and Y 1 represents a substituted or unsubstituted acyclic hydrocarbon group having 5 to 30 carbon atoms and —R From the group represented by '(OR') L- (wherein R 'independently represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and L is an integer of 1 to 20). One or more acyclic organic groups selected, n represents an integer of 1 to 8)
(B) component is a (meth) acrylate compound (B1) having an isocyanurate structure represented by the general formula (bI), and a (meth) acrylate compound represented by the following general formula (B-2) The (meth) acrylate-based composition according to claim 1 or 2, comprising one or more selected from (B2).

(In the formula (B-2), each G independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms, and each R 4 independently represents Each represents a hydrogen atom or a methyl group, and each R 5 independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group, and a represents an integer of 2 to 8 And each b is independently a positive number from 1 to 4. Z represents the following general formulas (b-II-1) to (b-II-6) and the above general formula (b-III) ) To any one of the organic groups represented by (b-VII).)

(In the above general formulas (b-II-1) to (b-II-6), each R 6 independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. And each R 7 independently represents a divalent organic group, p represents an integer of 0 to 4, q represents an integer of 0 to 3, and * represents a bonding portion.)
The (meth) acrylate composition according to claim 3, wherein the component (B1) is a (meth) acrylate compound having an isocyanurate structure represented by the following general formula (B-1).

(In the formula (B-1), each R 3 independently represents a hydrogen atom or a methyl group, and D 1 to D 3 each independently represents a divalent organic group.)
Furthermore, as the component (D), one or more selected from a reaction compound (D1) of an epoxy compound and (meth) acrylic acid and a urethane (meth) acrylate compound (D2) other than the compound corresponding to the component (B) The (meth) acrylate composition according to any one of claims 1 to 4, further comprising:
The (meth) acrylate composition according to claim 5, wherein the content of the component (D) is 2 to 50 parts by mass with respect to 100 parts by mass in total of the components (A) to (C).
The component (B1) is contained as the component (B), and the content of the component (B1) is 20 to 80% by mass based on the total amount of the components (A) to (C). The (meth) acrylate-type composition in any one of.
The component (B) includes the component (B1) and the component (B2), and the content of the component (B2) is 5 to 40% by mass with respect to the total amount of the components (A) to (C). The (meth) acrylate composition according to claims 3 to 7.
(Meth) according to any one of claims 3 to 7, comprising (B1) component as component (B) and having a viscosity at 25 ° C of 1000 to 50000 mPa · s of the (meth) acrylate composition. Acrylate composition.
The component (B) contains a component (B2), and the content of the component (B2) is 30 to 85% by mass with respect to the total amount of the components (A) to (C). The (meth) acrylate composition according to claim 1.
The composition according to any one of claims 3 to 6 and claim 10, wherein the component (B2) is contained as the component (B), and the viscosity of the (meth) acrylate composition at 25 ° C is 500 to 50,000 mPa · s. (Meth) acrylate-based composition.
The (meth) of claim 1 or 2, wherein the component (B) comprises a (meth) acrylate compound (B3) having a phenyl group represented by the following general formula (B-3a) or (B-3b): Acrylate composition.

(In the formulas (B-3a) and (B-3b), each X 1 independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms; a represents a divalent organic group, R 22 and R 23 each independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group, and R 4a , R 4b each independently represents a hydrogen atom or a methyl group, and R 6 to R 13 each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. A and b each represent an added mole number of alkylene oxide, each being a positive number, and an average value of a + b is 2 to 4. c represents an integer of 1 to 5, and d represents 1 to 5 Represents an integer, and e represents an integer of 1 to 5.)
The organic group Y a in the general formula (B-3a) or (B-3b) is —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —SO 2 —, —CH 2 —, The (meth) acrylate-based composition according to claim 12, which is either —O— or —CO—.
The (meth) acrylate-based composition according to claim 12 or 13, further comprising (meth) acrylate compound (B2 ′) represented by the following general formula (B-2a) as component (B).

(In the formula (B-2a), Z represents a divalent organic group represented by the general formula (b-III), and R 14 and R 15 each independently represents an alkylene having 1 to 4 carbon atoms. R 16 and R 17 each independently represents a hydrogen atom or a methyl group, and f and g represent the number of added moles of alkylene oxide, each being a positive number, and the average value of f + g is 2-4.)
15. The mass ratio of the content of the component (B3) and the content of the component (B2 ′) [(B3) component / (B2 ′) component] is 15/85 to 40/60. (Meth) acrylate composition.
The (meth) acrylate composition according to any one of claims 12 to 15, wherein the content of the component (A) is 5 to 40% by mass with respect to the total amount of the components (A) to (C).
The (meth) acrylate composition according to any one of claims 12 to 16, wherein the viscosity at 25 ° C is 300 to 50000 mPa · s.
A resin obtained by polymerizing the (meth) acrylate composition according to any one of claims 1 to 17.
A molded body formed by molding the resin according to claim 18.
The molded article according to claim 19, wherein the total luminous transmittance of the molded article is 85% or more.
The molded article according to claim 19 or 20, wherein the molded article has a refractive index of 1.45 or more at the d-line.
The molded body according to any one of claims 19 to 21, wherein the molded body has an Abbe number of 60 or less at d-line.
The molded body according to any one of claims 19 to 22, wherein the molded body is an optical component.