JP2012097199A - Half-cured product, cured product and methods for producing these, optical part, and curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cured product having heat resistance high enough to be used in a reflow process, with which generation of burr is suppressed by controlling deformation of half-cured products, and the rate of non-defective products is high after molding.SOLUTION: This method for producing a cured product includes a step of obtaining a half-cured product with 10-10(mPa s) complex viscosity at 25°C and 10 Hz frequency by exposing a curable composition to light and a heat-polymerizing step of obtaining the cured product by putting the half-cured product in a mold to be pressure-deformed and heating it to be thermally polymerized. The curable composition contains: a monomer having two or more radical polymerizable groups, namely a nonconjugated vinyl group, a nonconjugated (meth)allyl group or a nonconjugated isopropenyl group; a (meth)acrylate monomer, a photoradical polymerization initiator and a heat radical polymerization initiator, provided that any monomer corresponding to the monomer, having two or more polymerizable groups, namely a nonconjugated vinyl group, a nonconjugated (meth)allyl group or a nonconjugated isopropenyl group, is not contained in the (meth)acrylate monomer.

Description

  The present invention relates to a semi-cured product, a cured product, a production method thereof, an optical component, and a cured resin composition.

  Conventionally, from the viewpoint of excellent optical characteristics, mechanical strength, etc., inorganic glass materials are generally used as optical components (also referred to as optical elements, mainly lenses). As miniaturization progresses, miniaturization of optical elements becomes necessary, and it becomes difficult to produce inorganic glass materials having a large curvature (R) or complicated shapes due to workability problems. Yes.

  For this reason, plastic materials that are easy to process have been studied and used. Examples of plastic materials that can be easily processed include thermoplastic resins having good transparency, such as polyolefin, polymethyl methacrylate, polycarbonate, and polystyrene.

  On the other hand, when an IC (Integrated Circuits) chip or other electronic component is mounted on a circuit board, a metal paste (for example, solder paste) is applied (potted) in advance to a predetermined position on the circuit board, and the electronic component is placed at that position. A technology for manufacturing an electronic module at a low cost and at a high density has been developed by a technique of subjecting the circuit board to a reflow process (heating process) in a state where the circuit board is placed and mounting electronic components on the circuit board.

  In recent years, the above-described solder reflow processing is performed as an optical module integrated with an optical element in a state where an optical element is further mounted on a circuit board in addition to an electronic component, thereby producing an imaging device production system. Therefore, further improvement in production efficiency is desired.

  Of course, in an optical module manufactured by a production system incorporating the above-described reflow process, it is desired to use a plastic optical element that can be manufactured at low cost rather than a high-cost glass optical element. .

  However, thermoplastic resins that have been used as conventional resin materials for optical elements have good processability because they are softened and melted at a relatively low temperature, but the molded optical elements are easily deformed by heat. It has. When an electronic component incorporating an optical element is mounted on a substrate by a solder reflow process, the optical element itself is exposed to heating conditions of, for example, about 270 ° C., but an optical element made of a thermoplastic resin having low heat resistance. In the element, the shape deteriorates, which becomes a problem. Therefore, it has been demanded that an optical member using plastic is provided with heat resistance that can withstand a reflow process and is disposed on a substrate simultaneously with other electronic elements to reduce manufacturing costs.

  On the other hand, a method using a photocurable resin is known as a plastic material for an optical element used in an imaging element manufactured in a reflow process (see, for example, Patent Document 1). In general, a photocurable resin is in a liquid state or exhibits fluidity before curing, has good processability like a thermoplastic resin, and does not exhibit fluidity like a thermoplastic resin after curing. Therefore, deformation due to heat is small. However, the photo-curing resin has a low viscosity before curing, and the resin leaks from the mold joint (parting line) at the time of molding, and the leaked resin is cured and an unnecessary portion is simultaneously formed. There was a problem. Such leaked resin forms, for example, a thin film generally called a so-called burr, and other rod-like, spherical or angular protrusions, etc., but these are collectively referred to as “ It is called “Bali”.

  As a method for suppressing mold clearance leakage in order to suppress the formation of burrs during molding, in Patent Document 1, the curable composition is semi-cured by UV irradiation to produce a semi-cured product (gummy shape), and then the mold is removed. It proposes a manufacturing method in which pressure is applied and heat-cured. Specifically, in the examples of the document, polyacrylic acid soda (or sulfonic acid copolymer) which is a general thickener is used by using 2-alkyl-2-adamantyl (meth) acrylate as a curable resin. Combined), a photopolymerization initiator, a cured resin composition to which a thermal polymerization initiator has been added. After increasing the viscosity by light irradiation, it is cured by applying heat to suppress burrs during molding. Is disclosed.

Patent Document 2 discloses a technique for obtaining a cured product having a fine shape accurately formed by photopolymerizing a composition containing a compound having an alicyclic hydrocarbon skeleton and a radical polymerizable group. This document describes that a compound having two or more radically polymerizable groups may be blended, or that photopolymerization and thermal polymerization may be combined. However, as a specific example of selecting these, a composition containing dimethylol tricyclo [5.2.1.0 ^2,5 ] decanedimethacrylate, pentaerythritol triacrylate, a photopolymerization initiator and a thermal polymerization initiator is used. Only examples of using photopolymerization and thermal polymerization in this order are described (see Example 6).

  Patent Document 3 discloses a technique for curing a silicone-based resin composition containing an unsaturated bond-containing polyorganosylceroxyoxane, an alicyclic diacrylate, and a vinyl monomer. According to this document, it is described that a molded article excellent in transparency, heat resistance, water resistance and mechanical resistance can be obtained by using the silicone resin composition. However, as examples, only examples of photocuring a silicone resin composition containing caged silylated polyphenylsilsesquioxane, trimethylolpropane triacrylate, dicyclopentanyl diacrylate and a photopolymerization initiator are described. Not.

JP 2009-126011 A JP 2003-286316 A JP 2004-123936 A

The present inventors examined the method described in Patent Document 1 as a method for producing such a (meth) acrylate-based cured resin with improved heat resistance. Here, in the paragraph [0074] in the same document, the “moderate” viscosity after UV irradiation is 600 to 3000 cP (6 × 10 ² mPa · s to ³ × 10 ³ mPa · s). There is a description that the term “chemical conversion” means that the viscosity is 10,000 cP or more (1 × 10 ⁴ mPa · s or more). Further, according to Examples [Table 1] to [Table 4] in the same document, the moldability evaluation is impossible when the viscosity after UV irradiation is “high, gelation”, and the resin composition is It is disclosed that gelation has failed and the mold cannot be filled, making molding impossible. On the other hand, it is disclosed that the occurrence of burrs during molding can be suppressed if the viscosity after UV irradiation is “moderate”. However, the present inventors have studied under conditions where the viscosity after UV irradiation is “moderate”, it is difficult to control the deformability of the semi-cured product, and there is still dissatisfaction from the viewpoint of suppressing the occurrence of burrs during molding. In addition, the ratio of occurrence of cracks and wrinkles after molding was high (that is, the yield rate was low), and a lens having good transferability could not be obtained.

The inventors also studied the methods described in Patent Document 2 and Patent Document 3. As a result, the method described in Patent Document 2 can be shaped when a fine structure is formed on the surface, but cannot be shaped when a relatively large molded product such as a camera lens is desired. found. Moreover, since the method described in Patent Document 3 is cured in one step, it is impossible to impart a shape during curing, and it cannot be used for a lens or the like because the refractive index of the molded product is low. It has been found.
The present invention aims to solve the above problems. That is, the problem to be solved by the present invention is to control the deformability of the semi-cured product, thereby suppressing the generation of burrs during molding, high yield rate after molding, and heat resistance to the extent used in the reflow process. It is providing the manufacturing method of hardened | cured material with high property.

  As a result of intensive research, the inventors have surprisingly gelled when a specific vinyl polyfunctional monomer is blended and the complex viscosity of the semi-cured product obtained after UV irradiation is controlled within a specific range. It was found that a cured resin excellent in semi-cured state controllability despite being in a state and excellent in heat resistance can be obtained through a subsequent thermal polymerization step. While not being bound by any theory, the present invention controls the degree of deformation of the semi-cured product and the reflow process by controlling the three-dimensional structure by chain transfer during polymerization of the vinyl polyfunctional monomer. The heat resistance necessary for the optical component can be imparted to the optical component, and the above-described problems can be solved. That is, the present inventors have found that the above problems can be achieved by the following configuration, and have completed the present invention.

（一般式（１）中、Ｒ¹はラジカル重合性基を含む官能基を表し、Ｒ²は単結合または（ｎ＋１）価の飽和連結基を表し、ｎは１〜８の整数を表す。）
［３］ 前記一般式（１）のＲ¹が（メタ）アクリロイルオキシ基またはビニル基である［２］に記載の硬化物の製造方法。
［４］ 前記一般式（１）のＲ²が、炭素原子、水素原子および酸素原子からなる群より選択される１以上の原子から構成される連結基である［２］または［３］に記載の硬化物の製造方法。
［５］ 前記一般式（１）のｎが１〜４の整数である［２］〜［４］のいずれか一項に記載の硬化物の製造方法。
［６］ 前記２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマーが下記一般式（２）で表される［１］に記載の硬化物の製造方法。

（一般式（２）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹²は単結合または炭素数１〜１０の飽和炭化水素連結基を表す）
［７］ 前記（メタ）アクリレートモノマーが、多官能（メタ）アクリレートモノマーであるか、あるいは、多官能（メタ）アクリレートモノマーと単官能（メタ）アクリレートモノマーの混合物である［１］〜［６］のいずれか一項に記載の硬化物の製造方法。
［８］ 前記（メタ）アクリレートモノマーが、脂環構造を有している（メタ）アクリレートモノマーを含む［１］〜［７］のいずれか一項に記載の硬化物の製造方法。
［９］ 前記硬化樹脂組成物が、前記硬化性樹脂組成物に対して、前記２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマーを０．５〜３５重量％含有する［１］〜［８］のいずれか一項に記載の硬化物の製造方法。
［１０］ 前記（メタ）アクリレートモノマーが、多官能（メタ）アクリレートモノマーと単官能（メタ）アクリレートモノマーからなり、前記多官能（メタ）アクリレートモノマーと前記単官能（メタ）アクリレートモノマーとの総量に対し、前記多官能（メタ）アクリレートモノマーを３０〜９０重量％含有する［１］〜［９］のいずれか一項に記載の硬化物の製造方法。
［１１］ さらに非共役ビニル基を側鎖に有する重合体を含む［１］〜［１０］のいずれか一項に記載の硬化物の製造方法。
［１２］ 前記硬化性樹脂組成物の総量に対し、非共役ビニル基を側鎖に有する重合体を５〜５０質量％含有する［１１］に記載の硬化物の製造方法。
［１３］ ［１］〜［１２］のいずれか一項に記載の硬化物の製造方法によって製造された硬化物。
［１４］ 前記硬化物が、波長５８９ｎｍにおける屈折率が１．４５以上であり、アッベ数が４５以上であり、波長５８９ｎｍにおける厚さ１ｍｍ換算の光線透過率が７５％以上である［１３］に記載の硬化物。
［１５］ ［１３］または［１４］に記載の硬化物を用いた光学部品。
［１６］ ２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマー、（メタ）アクリレートモノマー、非共役ビニル基を側鎖に有する重合体、光ラジカル重合開始剤および熱ラジカル重合開始剤を含有する硬化樹脂組成物（ただし、前記（メタ）アクリレートモノマーには、２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマーに該当するものは含まれない）。
［１７］ 前記２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマーが下記一般式（２）で表される［１６］に記載の硬化樹脂組成物。

（一般式（２）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹²は単結合または炭素数１〜１０の飽和炭化水素連結基を表す）
［１８］ ２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマー、（メタ）アクリレートモノマー、光ラジカル重合開始剤および熱ラジカル重合開始剤を含有する硬化樹脂組成物に対して光照射して、２５℃、周波数１０Ｈｚにおける複素粘度が１０⁵〜１０⁸ｍＰａ・．ｓの半硬化物を製造する方法（ただし、前記（メタ）アクリレートモノマーには、２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマーに該当するものは含まれない）。
［１９］ ［１８］に記載の半硬化物の製造方法によって製造された半硬化物。
［２０］ ２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマー、（メタ）アクリレートモノマーおよび光ラジカル重合開始剤を含有する硬化樹脂組成物に対して光照射して、２５℃、周波数１０Ｈｚにおける複素粘度が１０⁵〜１０⁸ ｍＰａ・ｓの半硬化物を形成する方法（但し、前記（メタ）アクリレートモノマーには、２つ以上のラジカル重合性基を有し、非共役ビニル基、非共役（メタ）アリル基もしくは非共役イソプロペニル基を含むモノマーに該当するものは含まれない）。 [1] Monomer having two or more radical polymerizable groups and containing non-conjugated vinyl group, non-conjugated (meth) allyl group or non-conjugated isopropenyl group, (meth) acrylate monomer, photo radical polymerization initiator and heat Irradiating the cured resin composition containing the radical polymerization initiator with light to obtain a semi-cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz; A method of producing a cured product comprising a heat polymerization step of obtaining a cured product by applying pressure deformation to a mold and heating to thermally polymerize (however, the (meth) acrylate monomer includes two or more radical polymerizations) And a monomer having a non-conjugated vinyl group, non-conjugated (meth) allyl group, or non-conjugated isopropenyl group).
[2] A monomer having two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl group is represented by the following general formula (1) [1] ] The manufacturing method of the hardened | cured material of description.

(In general formula (1), R ¹ represents a functional group containing a radical polymerizable group, R ² represents a single bond or a (n + 1) -valent saturated linking group, and n represents an integer of 1 to 8).
[3] The method for producing a cured product according to [2], wherein R ^{1 in the} general formula (1) is a (meth) acryloyloxy group or a vinyl group.
[4] [2] or [3], wherein R ^{2 in the} general formula (1) is a linking group composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. A method for producing a cured product.
[5] The method for producing a cured product according to any one of [2] to [4], wherein n in the general formula (1) is an integer of 1 to 4.
[6] A monomer having two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl group is represented by the following general formula (2) [1] ] The manufacturing method of the hardened | cured material of description.

(In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a single bond or a saturated hydrocarbon linking group having 1 to 10 carbon atoms)
[7] The (meth) acrylate monomer is a polyfunctional (meth) acrylate monomer or a mixture of a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate monomer [1] to [6] The manufacturing method of the hardened | cured material as described in any one of these.
[8] The method for producing a cured product according to any one of [1] to [7], wherein the (meth) acrylate monomer includes a (meth) acrylate monomer having an alicyclic structure.
[9] The curable resin composition has two or more radical polymerizable groups with respect to the curable resin composition, and is a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl. The manufacturing method of the hardened | cured material as described in any one of [1]-[8] which contains the monomer containing group 0.5 to 35weight%.
[10] The (meth) acrylate monomer is composed of a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate monomer, and the total amount of the polyfunctional (meth) acrylate monomer and the monofunctional (meth) acrylate monomer. On the other hand, the manufacturing method of the hardened | cured material as described in any one of [1]-[9] which contains the said polyfunctional (meth) acrylate monomer 30 to 90weight%.
[11] The method for producing a cured product according to any one of [1] to [10], further including a polymer having a non-conjugated vinyl group in the side chain.
[12] The method for producing a cured product according to [11], containing 5 to 50% by mass of a polymer having a non-conjugated vinyl group in a side chain with respect to the total amount of the curable resin composition.
[13] A cured product produced by the method for producing a cured product according to any one of [1] to [12].
[14] The cured product has a refractive index of 1.45 or more at a wavelength of 589 nm, an Abbe number of 45 or more, and a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 75% or more. Hardened | cured material of description.
[15] An optical component using the cured product according to [13] or [14].
[16] A monomer having two or more radically polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl group, a (meth) acrylate monomer, and a non-conjugated vinyl group as a side chain A cured resin composition containing a polymer having a photo radical polymerization initiator and a thermal radical polymerization initiator (wherein the (meth) acrylate monomer has two or more radical polymerizable groups and is a non-conjugated vinyl). Groups, non-conjugated (meth) allyl groups, or monomers containing non-conjugated isopropenyl groups are not included).
[17] A monomer having two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl group is represented by the following general formula (2) [16] ] The cured resin composition as described in.

(In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a single bond or a saturated hydrocarbon linking group having 1 to 10 carbon atoms)
[18] A monomer having two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl group, a (meth) acrylate monomer, a photo radical polymerization initiator, and heat The cured resin composition containing the radical polymerization initiator is irradiated with light, and the complex viscosity at 25 ° C. and a frequency of 10 Hz is 10 ⁵ to 10 ⁸ mPa ·. a process for producing a semi-cured product of s (wherein the (meth) acrylate monomer has two or more radical polymerizable groups, and is a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl) It does not include those corresponding to monomers containing groups).
[19] A semi-cured product produced by the method for producing a semi-cured product according to [18].
[20] Contains a monomer having two or more radical polymerizable groups, a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl group, a (meth) acrylate monomer, and a photo radical polymerization initiator The cured resin composition to be irradiated with light to form a semi-cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz (however, in the (meth) acrylate monomer, It does not include those corresponding to monomers having two or more radically polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl group).

  According to the present invention, by controlling the deformability of the semi-cured product, the occurrence of burrs during molding is suppressed, the yield of non-defective products after molding is high, and the cured product has high heat resistance to the extent that it is used in the reflow process. A manufacturing method can be provided.

In the following, the semi-cured product and the cured product of the present invention, their production methods, materials used therefor, and the like will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. In addition, since the manufacturing method of the hardened | cured material of this invention includes the manufacturing method of the semi-hardened material of this invention, it describes in the manufacturing method column of the semi-hardened material of this invention about the preferable aspect of the manufacturing method common to both.

[Method for producing semi-cured product]
The method for producing a semi-cured product of the present invention includes a monomer having two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl group (hereinafter referred to as “vinyl-based”). It is also referred to as “polyfunctional monomer”), a cured resin composition containing a (meth) acrylate monomer, a photoradical polymerization initiator and a thermal radical polymerization initiator is irradiated with light, and the complex viscosity at 25 ° C. and a frequency of 10 Hz is 10 Including a step of obtaining a semi-cured product of ⁵ to 10 ⁸ mPa · s (however, the (meth) acrylate monomer has two or more radical polymerizable groups, a non-conjugated vinyl group, a non-conjugated (meth) It does not include monomers corresponding to monomers containing an allyl group or a non-conjugated isopropenyl group).
Here, in the present specification, the “semi-cured product” is a product obtained by polymerizing a cured resin composition, which is not completely solid and has a certain degree of fluidity. For example, the photopolymer of the cured resin composition having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz is a semi-cured product. Although it does not specifically limit this invention, the thing of 1.0x10 < ⁹ > mPa * s is considered as a semi-hardened | cured material as an upper limit of the complex viscosity in 25 degreeC and the frequency of 10 Hz. On the other hand, the “cured product” means a product obtained by polymerizing a cured resin composition and in a completely solid state.
Hereafter, each material used for the manufacturing method of the semi-hardened material of this invention and the method of light irradiation (it is also called a photopolymerization process) are demonstrated in order.

<Vinyl polyfunctional monomer>
The cured resin composition used in the production method of the present invention contains a vinyl polyfunctional monomer.
In the present invention, by using such a cured resin composition containing a vinyl polyfunctional monomer, the viscosity of the semi-cured product after photopolymerization is controlled within a specific range, and the semi-cured product is described later. The heat resistance and non-defective rate of the cured product obtained by thermal polymerization in the method for producing a cured product of the invention can be improved.

  The vinyl polyfunctional monomer contained in the cured resin composition used in the production method of the present invention preferably has 2 to 12 radical polymerizable groups in one molecule, and has 2 to 8 radical polymerizable groups. More preferably, 2-4 are more preferable, and two are most preferable. In addition, it is essential that at least one of the radical polymerizable groups contained in the vinyl polyfunctional monomer is any one of a non-conjugated vinyl group, a non-conjugated (meth) allyl group, and a non-conjugated isopropenyl group. However, among these, those containing a non-conjugated vinyl group are preferable. Two or more radically polymerizable groups contained in the vinyl polyfunctional monomer may be the same as or different from each other. The case where they are different is preferable, and the combination in that case is preferably a combination of a non-conjugated vinyl group and a (meth) acryloyloxy group. By adopting different radical polymerizable groups, it is possible to effectively suppress thermal coloring of the cured product.

（一般式（１）中、Ｒ¹はラジカル重合性基を含む官能基を表し、Ｒ²は単結合または（ｎ＋１）価の飽和連結基を表し、ｎは１〜８の整数を表す。）
前記Ｒ¹が表すラジカル重合性基に特に制限はなく、例えば、以下の置換基を用いることができる。（メタ）アクリル基、非共役（メタ）アリル基、非共役ビニル基、非共役イソプロペニル基、ビニルエーテル基、アリルエーテル基。
その中でも前記Ｒ¹は、非共役ビニル基、非共役（メタ）アリル基、非共役イソプロペニル基または（メタ）アクリロイルオキシ基であることが好ましく、非共役ビニル基または（メタ）アクリロイルオキシ基であることがより好ましく、（メタ）アクリロイルオキシ基であることがさらに好ましい。 The vinyl polyfunctional monomer used in the present invention is preferably a monomer represented by the following general formula (1).

(In general formula (1), R ¹ represents a functional group containing a radical polymerizable group, R ² represents a single bond or a (n + 1) -valent saturated linking group, and n represents an integer of 1 to 8).
There is no particular limitation on the radical polymerizable group which the R ¹ represents, for example, may use the following substituents. (Meth) acryl group, non-conjugated (meth) allyl group, non-conjugated vinyl group, non-conjugated isopropenyl group, vinyl ether group, allyl ether group.
Among these, R ¹ is preferably a non-conjugated vinyl group, a non-conjugated (meth) allyl group, a non-conjugated isopropenyl group or a (meth) acryloyloxy group, and is a non-conjugated vinyl group or a (meth) acryloyloxy group. More preferably, it is more preferably a (meth) acryloyloxy group.

Said n represents the integer of 1-8, Preferably it is an integer of 1-3, More preferably, it is 1 or 2, More preferably, it is 1. When n is 2 or more, two or more R ^{1 s} may be the same as or different from each other. Preferred is when at least one of the two or more R ¹ is a (meth) acryloyloxy group.

The (n + 1) -valent saturated linking group represented by R ² is not particularly limited, and is, for example, a saturated linking group composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, and a sulfur atom. Can be used. The saturated linking group is more preferably a saturated linking group composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom and an oxygen atom. Further, a saturated linking group consisting of a carbon atom and a hydrogen atom is more preferable.
Examples of the (n + 1) -valent saturated linking group represented by R ² include a saturated linking group containing an alkylene structure, an alkyleneoxy structure, an alkylenethio structure or a saturated cyclic structure. For example, examples of the divalent saturated linking group include an alkylene group, an alkyleneoxyalkylene group, and a polyalkyleneoxyalkylene group. The number of atoms constituting the linking chain of these saturated linking groups is 1 to 25. It is preferably 1 to 15, more preferably 1 to 15, and still more preferably 1 to 10. Further, when the saturated linking group includes a saturated cyclic structure, the saturated cyclic structure may be any of a spiro cyclic structure, a cardo cyclic structure, and a fused cyclic structure, and a spiro cyclic structure can be given as a preferred example.

（一般式（２）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹²は単結合または炭素数１〜１０の飽和炭化水素連結基を表す） The vinyl polyfunctional monomer used in the present invention is more preferably a monomer represented by the following general formula (2).

(In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a single bond or a saturated hydrocarbon linking group having 1 to 10 carbon atoms)

The saturated hydrocarbon linking group represented by R ¹² preferably has 0 to 22 carbon atoms, more preferably 0 to 16 carbon atoms, and still more preferably 1 to 9 carbon atoms. The saturated hydrocarbon linking group represented by R ¹² may include a cyclic structure, but a chain-like saturated hydrocarbon linking group is preferred.

In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Examples of the substituent that can be employed as the substituent in the general formula (1) and the general formula (2) include an alkyl group, an alkoxy group, a halogen group, a halogenated alkyl group, a hydroxyl group, a hydroxyalkyl group, a thiol group, and an alkylthiol. Examples include groups. Of these, an alkyl group is preferable.

  Specific examples of the vinyl polyfunctional monomer preferably used in the present invention are listed below, but the vinyl polyfunctional monomer that can be used in the present invention is not limited to the following compounds.

Vinyl polyfunctional monomer

(Molecular weight)
The molecular weight of the vinyl polyfunctional monomer is preferably 100 to 500, more preferably 120 to 350, and particularly preferably 150 to 300.

(how to get)
There is no restriction | limiting in particular about the acquisition method of these said vinyl type polyfunctional monomers, You may obtain commercially and may manufacture by synthesis | combination.
When commercially available, for example, NK Economer AL, NK Economer ML, NK Economer ML4G, NK Economer ML8G, NK Economer ML12G (manufactured by Shin-Nakamura Chemical Co., Ltd.) can be preferably used.
When producing by synthesis, the method for producing the vinyl polyfunctional monomer is not particularly limited, and can be synthesized by a known method. For example, when synthesizing the compound (C-1) that can be preferably used in the present invention among the vinyl-based polyfunctional monomers, Bulletin of the Chemical Society of Japan, 2003, vol. 76, # 7 P.R. It can be synthesized by the method described in 1441-1446.

In the method for producing a semi-cured product of the present invention, the cured resin composition preferably contains 0.5 to 35% by mass of the vinyl polyfunctional monomer with respect to a (meth) acrylate monomer described later, The content is more preferably 35% by mass, and particularly preferably 10 to 33% by mass.
In the method for producing a semi-cured product of the present invention, the cured resin composition preferably contains 0.5 to 30% by mass of the vinyl polyfunctional monomer with respect to the total amount of the cured resin composition. It is more preferable to contain 5-25 mass%, and it is especially preferable to contain 10-20 mass%.

<(Meth) acrylate monomer>
The method for producing a semi-cured product of the present invention includes a (meth) acrylate monomer. In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 1,000 or less.

（一般式（３）中、Ｌ¹は単結合または２価の連結基を表し、Ｂ¹は１価の脂環基を表す。）
前記Ｌ¹は、単結合または２価のアルキレン基であることが好ましく、単結合またはメチレン基であることがより好ましく、単結合であることが特に好ましい。
前記Ｂ¹は炭素数５〜１５の１価の脂環基であることが好ましく、炭素数６〜１５の１価の脂環基であることがより好ましく、炭素数８〜１２の１価の脂環基であることが特に好ましい。前記Ｂ¹は２以上の環が縮合した縮合環であることが好ましく、２または３の環が縮合した縮合環であることがより好ましい。また、前記Ｂ¹は脂環構造中に二重結合を有していないことが好ましい。 In the method for producing a semi-cured product of the present invention, the (meth) acrylate monomer preferably includes a (meth) acrylate monomer having an alicyclic structure. That is, the (meth) acrylate monomer is preferably represented by the following general formula (3) or (4).

(In General Formula (3), L ¹ represents a single bond or a divalent linking group, and B ¹ represents a monovalent alicyclic group.)
L ¹ is preferably a single bond or a divalent alkylene group, more preferably a single bond or a methylene group, and particularly preferably a single bond.
B ¹ is preferably a monovalent alicyclic group having 5 to 15 carbon atoms, more preferably a monovalent alicyclic group having 6 to 15 carbon atoms, and a monovalent alicyclic group having 8 to 12 carbon atoms. Particularly preferred is an alicyclic group. B ¹ is preferably a condensed ring in which two or more rings are condensed, and more preferably a condensed ring in which two or three rings are condensed. In addition, the B ¹ represents preferably does not have a double bond in the alicyclic structure.

（一般式（４）中、Ｌ²およびＬ³はそれぞれ独立に単結合または２価の連結基を表し、Ｂ²は２価の脂環基を表す。）
前記Ｌ²およびＬ³はそれぞれ独立に単結合または２価のアルキレン基であることが好ましく、単結合またはメチレン基であることがより好ましく、メチレン基であることが特に好ましい。
前記Ｂ²は炭素数５〜１５の２価の脂環基であることが好ましく、炭素数６〜１５の２価の脂環基であることがより好ましく、炭素数８〜１２の２価の脂環基であることが特に好ましい。前記Ｂ¹は２以上の環が縮合した縮合環であることが好ましく、２または３の環が縮合した縮合環であることがより好ましい。また、前記Ｂ²は脂環構造中に二重結合を有していないことが好ましい。

(In General Formula (4), L ² and L ³ each independently represent a single bond or a divalent linking group, and B ² represents a divalent alicyclic group.)
L ² and L ³ are each independently preferably a single bond or a divalent alkylene group, more preferably a single bond or a methylene group, and particularly preferably a methylene group.
B ² is preferably a divalent alicyclic group having 5 to 15 carbon atoms, more preferably a divalent alicyclic group having 6 to 15 carbon atoms, and a divalent alicyclic group having 8 to 12 carbon atoms. Particularly preferred is an alicyclic group. B ¹ is preferably a condensed ring in which two or more rings are condensed, and more preferably a condensed ring in which two or three rings are condensed. Further, the B ² preferably does not have a double bond in the alicyclic structure.

  The said (meth) acrylate monomer used for the manufacturing method of the semi-hardened | cured material of this invention can be divided into a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate monomer. Here, the polyfunctional (meth) acrylate monomer means a (meth) acrylate monomer having a plurality of functional groups, and the monofunctional (meth) acrylate monomer is a (meth) acrylate monomer having one functional group. Say that. In the present specification, “functional group of (meth) acrylate monomer” refers to an ethylenically unsaturated bond involved in the polymerization reaction.

(Multifunctional (meth) acrylate monomer)
As the polyfunctional (meth) acrylate monomer used in the present invention, for example, the following can be used.
Tricyclodecane dimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, cyclohexane di (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) ) Acrylic isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6- Hexanediol di (meth) acrylate, allyloxy polyethylene glycol (meth) acrylate, 1,9-nonanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexahydrophthalic acid di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, propylene oxide (hereinafter referred to as “PO”) modified neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) Acrylate, ECH-modified phthalic acid di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylol propane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di ( (Meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, ECH modified glycerol tri (meth) acrylate, EO modified glycerol tri (meth) acrylate, PO modified glycerol tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, EO-modified phosphate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylo Propane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipenta Erythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol Rutetora (meth) acrylate.
Among them, in the present invention, it is preferable to use a polyfunctional (meth) acrylate monomer having an alicyclic structure, and a polyfunctional (meth) acrylate monomer having a condensed alicyclic structure, such as tricyclodecane dimethanol di (meth). Acrylates are more preferred, and tricyclodecane dimethanol diacrylate is particularly preferred.

(Monofunctional (meth) acrylate monomer)
As the monofunctional (meth) acrylate monomer used in the present invention, for example, the following can be used.
Dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, adamantyl (meth) acrylate, methyladamantyl methacrylate and ethyladamantyl (meth) acrylate adamantyl (meth) acrylates such as isobornyl (meth) norbornyl (meth) acrylates such as acrylate, tricyclo [5,2,1,0 ^2,6] tricyclodecane such dec-8-yl acrylate (meth) Acrylates, 2-ethyl-2-butylpropanediol (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (Meth) acrylate, 1- or 2-naphthyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter “EO”) Cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl ( (Meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy Triethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxy Ethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate Tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate.
Among them, in the present invention, it is preferable to use a monofunctional (meth) acrylate monomer having an alicyclic structure having no multiple bond, and a monofunctional (meth) acrylate monomer having a condensed alicyclic structure, such as 1-adamantyl. (meth) acrylate, isobornyl (meth) acrylate and tricyclo [5,2,1,0 ^2,6] dec-8-yl (meth) acrylate are more preferable, 1-adamantyl methacrylate are particularly preferred.

In the method for producing a semi-cured product of the present invention, the (meth) acrylate monomer may be a polyfunctional (meth) acrylate monomer or a mixture of a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate monomer. preferable.
Among them, the (meth) acrylate monomer is a mixture of a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate monomer, from the viewpoint of improving the heat resistance of the cured product after thermal polymerization described below. More preferred.
Furthermore, it is preferable to contain 30-90 mass% of said polyfunctional (meth) acrylate monomers with respect to the total amount of said polyfunctional (meth) acrylate monomer and said monofunctional (meth) acrylate monomer, 35-80 mass%. It is more preferable to contain, and it is especially preferable to contain 40-70 mass%.

  Specific examples of the (meth) acrylate monomer preferably used in the present invention are listed below, but the present invention is not limited to the following compounds.

Monofunctional (meth) acrylic monomer

(Molecular weight)
The molecular weight of the (meth) acrylate monomer preferably used in the present invention is preferably 100 to 500, more preferably 150 to 450, and particularly preferably 200 to 400.

  In the method for producing a semi-cured product of the present invention, the cured resin composition preferably contains 50 to 95% by mass of the (meth) acrylate monomer with respect to the total amount of the cured resin composition. % Is more preferable, and 60 to 90% by mass is particularly preferable.

(how to get)
There is no restriction | limiting in particular about the acquisition method of these said (meth) acrylate monomers, You may obtain commercially and may manufacture by synthesis | combination.
When commercially available, for example, NK ester DCP, NK ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be preferably used.
In the case of producing by synthesis, the production method of the (meth) acrylate monomer is not particularly limited, and can be synthesized by a known method. For example, when synthesizing the compound (Aa-1) that can be preferably used in the present invention among the (meth) acrylate monomers, the compound is synthesized by the method described in US6365771 B1 (2002, Nissan Chemical Industries, Ltd.). be able to.

<Radical radical polymerization initiator>
In the method for producing a semi-cured product of the present invention, the cured resin composition contains a radical photopolymerization initiator. There is no restriction | limiting in particular as said radical photopolymerization initiator, A well-known radical photopolymerization initiator can be used.

  As the radical photopolymerization initiator, specifically, the following compounds can be used. Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylbenzylphosphine oxide, bis (2,6-dimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,4) 6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1-phenyl 2-hydroxy-2methyl Propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1,2-diphenylethanedione, methylphenylglyoxylate.

  Among them, in the present invention, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) manufactured by BASF Corporation can be preferably used as the radical photopolymerization initiator.

  The addition amount of the radical photopolymerization initiator in the curable resin composition is not particularly limited, but the total amount of the curable resin composition (preferably, the (meth) acrylate monomer, the vinyl polyfunctional monomer, and the later-described amount). Is preferably 0.01 to 5% by mass, more preferably 0.05 to 2.5% by mass, based on the sum of the polymers having non-conjugated vinyl groups in the side chain. It is particularly preferably 8% by mass.

<Thermal radical polymerization initiator>
In the method for producing a semi-cured product of the present invention, the cured resin composition contains a thermal radical polymerization initiator. By adding such a thermal radical polymerization initiator to the cured resin composition in advance, the semi-cured product of the present invention can be easily converted into a cured product of the present invention having high heat resistance by thermal polymerization with good moldability and easily. It can be manufactured with high productivity.

  Specifically, the following compounds can be used as the thermal radical polymerization initiator. 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t- Hexyl peroxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, dicumyl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexano Ate, t-hexylperoxy-2-ethylhexanoate, cumene hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane.

  Among them, in the present invention, it is possible to preferably use Perbutyl O (t-butylperoxy-2-ethylhexanoate) and Parkmill H (cumene hydroperoxide) manufactured by NOF Corporation as the thermal radical polymerization initiator.

  The addition amount of the thermal radical polymerization initiator in the cured resin composition is not particularly limited, but the total amount of the cured resin composition (preferably, the (meth) acrylate monomer, the vinyl polyfunctional monomer, and the non-described later). Is preferably 0.01 to 5.00% by mass, more preferably 0.01 to 4.00% by mass, based on the total of the polymers having a conjugated vinyl group in the side chain. It is especially preferable that it is 05-0.2 mass%.

<Polymer having non-conjugated vinyl group in side chain>
The method for producing a semi-cured product of the present invention further includes a polymer having a non-conjugated vinyl group in the side chain, when the cured resin composition is directly placed on a thermoforming mold before light irradiation, This is preferable from the viewpoint of adjusting the viscosity of the cured resin composition before irradiation with light so that leakage to the mold clearance can be suppressed.

  Specific examples of the polymer having a non-conjugated vinyl group preferably used in the present invention in the side chain are listed below, but the present invention is not limited to the following compounds.

Polymer having non-conjugated vinyl group in side chain

(Molecular weight)
The molecular weight of the polymer having a non-conjugated vinyl group in the side chain of the present invention is preferably from 1,000 to 10,000,000, more preferably from 5,000 to 300,000, and particularly preferably from 10,000 to 200,000.

(Tg)
The glass transition temperature (hereinafter also referred to as Tg) of the polymer having a non-conjugated vinyl group in the side chain of the present invention is preferably 30 to 400 ° C, more preferably 50 to 350 ° C, and 60 to A temperature of 300 ° C. is particularly preferable.

  The method for producing a semi-cured product of the present invention comprises a total amount of the cured resin composition (preferably the (meth) acrylate monomer, the vinyl polyfunctional monomer, the photo radical polymerization initiator, the thermal radical polymerization initiator, and The total amount of the polymer having non-conjugated vinyl groups in the side chain) is preferably 5 to 50% by mass, and preferably 5 to 45% by mass of the polymer having the non-conjugated vinyl group in the side chain. Is more preferable, and it is especially preferable to contain 15-40 mass%. The content of the polymer having the non-conjugated vinyl group in the side chain with respect to the total amount of the cured resin composition is 50% by mass or less to suppress the initial viscosity of the cured resin composition before light irradiation. This is preferable from the viewpoint of facilitating dispensing.

<Other additives>
In the method for producing a semi-cured product of the present invention, the cured resin composition is a resin, monomer, dispersant, plasticizer, heat stabilizer, release agent, or the like that does not satisfy the conditions of the present invention unless it is contrary to the spirit of the present invention. Additives such as molds may be included.

<Light irradiation process>
The method for producing a semi-cured product of the present invention comprises a step of irradiating the cured resin composition with light to obtain a semi-cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz. Including.
In the method for producing a semi-cured product of the present invention, the cured resin composition may be directly installed on a thermoforming mold used when thermally polymerizing the cured resin composition before light irradiation in the method for producing a cured product of the present invention described later, Semi-curing after light irradiation obtained in the method for producing a cured product of the present invention, which will be described later, after producing a semi-cured product by putting the cured resin composition in a mold different from the mold for thermoforming during light irradiation The object may be moved to a thermoforming mold.

  Here, the thermoforming mold is generally configured to be able to be heated while pressing the contents by combining two molds, and when a low viscosity composition is injected into the thermoforming mold, It causes leakage to the mold clearance. The cured resin composition used in the method for producing a semi-cured product of the present invention generally has a low viscosity to be directly injected into a thermal mold. Therefore, in one preferred embodiment of the method for producing a semi-cured product of the present invention, as described above, a polymer having a non-conjugated vinyl group in the side chain is further added to adjust the viscosity of the cured resin composition, It is also preferable from the viewpoint of manufacturability to obtain a cured product by performing light irradiation and thermal polymerization described later in one mold for thermal forming.

On the other hand, in another preferred embodiment of the method for producing a semi-cured product of the present invention, the cured resin composition is placed in a mold different from the thermoforming mold during light irradiation, and the semi-cured product is produced. From the viewpoint of reducing the material cost, it is preferable to move the semi-cured product after light irradiation obtained in the method for producing a cured product of the present invention described later to a thermoforming mold.
Here, when using a mold different from the thermoforming mold, it is preferable to use a so-called preform mold. The preform mold may be made of metal, glass, or resin. Considering repeated use in the mass production process, the preform mold is preferably made of metal or glass. In addition, when the semi-cured product of the present invention is used as a lens, it is preferable that at least one surface of the preform mold has the same or close shape as the thermoforming mold. It is more preferable to have a shape that is the same as or close to the shape of the thermoforming mold.

(Light irradiation conditions)
Preferred conditions for light irradiation in the method for producing a semi-cured product of the present invention will be described below.
The light irradiation is preferably performed so that the complex viscosity of the semi-cured product after the light irradiation at 25 ° C. and a frequency of 10 Hz is 10 ⁵ to 10 ⁸ mPa · s, and is 10 ⁵ to 10 ^7.5 mPa · s. it is more preferable to carry out such, it is particularly preferred to carry out so that 10 ^5.5 ~10 ^7.0 mPa · s.

The light used for the light irradiation is preferably ultraviolet light or visible light, and more preferably ultraviolet light. For example, metal halide lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, sterilization lamps, xenon lamps, LED light source lamps, etc. are preferably used.
The atmosphere at the time of the light irradiation is preferably air or inert gas substitution, and more preferably nitrogen atmosphere until the oxygen concentration becomes 1% or less.

[Semi-cured product]
The semi-cured product of the present invention is produced by the method for producing a semi-cured product of the present invention. Such a semi-cured product can be preferably used in the method for producing a cured product of the present invention described later.

The semi-cured product of the present invention is obtained by polymerizing a composition containing a (meth) acrylate monomer and a vinyl polyfunctional monomer, has a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz, It is preferable that a radical polymerization initiator is included (however, the (meth) acrylate monomer does not include a vinyl polyfunctional monomer). Here, the preferable range of the complex viscosity of the semi-cured product of the present invention is the same as the preferable range of the complex viscosity of the semi-cured product in the above-described method for producing a semi-cured product of the present invention.

  In the semi-cured product of the present invention, after the light irradiation step, the radical photopolymerization initiator is completely consumed and may not be contained at all, or the radical photopolymerization initiator may remain. In the present invention, among them, it is preferable that no photoradical polymerization initiator is contained.

(Tg)
The glass transition temperature (hereinafter also referred to as Tg) of the semi-cured product of the present invention is preferably −150 to 0 ° C., more preferably −50 to 0 ° C., and −20 to 0 ° C. Is particularly preferred.

[Method of forming semi-cured product]
The present invention also relates to a method for forming a semi-cured product.
In the method for forming a semi-cured product of the present invention, a cured resin composition containing a (meth) acrylate monomer, a vinyl polyfunctional monomer and a photo radical polymerization initiator is irradiated with light at 25 ° C. and a frequency of 10 Hz. This is a method for forming a semi-cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s (however, the (meth) acrylate monomer does not include those corresponding to vinyl polyfunctional monomers).
With such a configuration, in the present invention, a semi-cured product having an appropriate complex viscosity can be formed.

[Method for producing cured product]
The method for producing a cured product of the present invention includes a monomer having two or more radical polymerizable groups, a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl group, a (meth) acrylate monomer, A step of obtaining a semi-cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz by irradiating light to a cured resin composition containing a photo radical polymerization initiator and a thermal radical polymerization initiator. (That is, a step of obtaining a semi-cured product by the method for producing a semi-cured product of the present invention), and a thermal polymerization step of obtaining a cured product by putting the semi-cured product into a mold, pressurizing and deforming, and heat-polymerizing And.

<Thermal polymerization process>
The manufacturing method of the hardened | cured material of this invention includes the thermal-polymerization process which puts the said semi-hardened | cured material in a metal mold | die, carries out pressure deformation, heats and heat-polymerizes, and obtains hardened | cured material.
The metal mold | die used with the manufacturing method of the hardened | cured material of this invention is also called the metal mold | die for thermoforming. In general, the thermoforming mold preferably has a configuration in which two molds can be combined and heated while pressing the contents. As such a thermoforming mold, for example, those described in JP-A-2009-126011, etc. can be used.

(Introduction to mold)
In the method for producing a cured product of the present invention, first, the semi-cured product produced by the method for producing a semi-cured product of the present invention is placed in a mold. First, the process of putting a semi-cured product into a mold will be described.
The semi-cured product after light irradiation is directly placed on the thermoforming mold and irradiated with light as described in the above-described method for producing a semi-cured product of the present invention. It is irradiated with light in another mold. When the semi-cured product after the light irradiation is directly placed on the thermoforming mold and irradiated with light, the operation itself is not particularly required to be put into the thermoforming mold, and it is described that it is put into the mold for explanation. There are only.
On the other hand, when the semi-cured product after light irradiation is placed in a mold different from the thermoforming mold and irradiated with light, it means a step of moving to the thermoforming mold. As a method for moving the semi-cured product after the light irradiation to the thermoforming mold, for example, a syringe, an air tweezer having a vacuum pad and a vacuum generator can be used. Since the semi-cured product of the present invention has a complex viscosity in a specific range, it can be easily moved to a thermoforming mold using a syringe or the like in this way.

(Pressure deformation / heating)
In the manufacturing method of the hardened | cured material of this invention, the semi-hardened material put into the metal mold | die is pressure-deformed, it heats and heat-polymerizes, and hardened | cured material is obtained.
Here, the pressure deformation and the heating may be performed at the same time, the heating may be performed after the pressure deformation, or the pressure deformation may be performed after the heating. It is preferable to carry out simultaneously. Further, it is also preferable that the pressure deformation and the heating are performed at the same time and the heating is further performed at a higher temperature after the pressure is stabilized.

The pressure in the pressurized and deformed is preferably ^{1kg / cm 2 ~100kg / cm 2} , more preferably ^{3kg / cm 2 ~50kg / cm 2} , is 3kg / cm ² ~30kg / cm ² It is particularly preferred.
The heating temperature is preferably 80 to 300 ° C, more preferably 120 to 300 ° C, and particularly preferably 150 to 280 ° C.
On the other hand, in the case of heating to a higher temperature after the pressure is stabilized, the temperature is preferably 80 to 300 ° C, more preferably 120 to 300 ° C, and particularly preferably 150 to 280 ° C.
The thermal polymerization time is preferably 30 to 1000 seconds, more preferably 30 to 500 seconds, and particularly preferably 60 to 300 seconds.
The atmosphere at the time of the thermal polymerization is preferably air or inert gas substitution, and more preferably nitrogen atmosphere until the oxygen concentration becomes 1% or less.

[Cured product]
The cured product of the present invention is produced by the method for producing a cured product of the present invention.
Hereinafter, preferable characteristics of the cured product of the present invention will be described.

(270 ° C storage elastic modulus)
The cured product of the present invention is characterized by high performance at 270 ° C. storage modulus and high heat resistance. Thus, the cured product of the present invention can be installed on a substrate together with a general electronic element and fixed by a reflow process because of its high performance at 270 ° C. storage elastic modulus. Manufacturing costs can be greatly reduced.
The cured product of the present invention is more able preferably 270 ° C. storage elastic modulus of ^{0.1 × 10 2 MPa~30 × 10 2} MPa, which is ^{1.0 × 10 2 MPa~30 × 10 2} MPa It is preferably 1.5 × 10 ² MPa to 30 × 10 ² MPa. In addition, the 270 degreeC storage elastic modulus in this invention is the value measured on conditions of tension mode, frequency 10Hz, and distortion 10micrometer (constant) using Rhegel-E4000 (The UBM Co., Ltd. dynamic viscoelasticity measuring apparatus). Is used.

(Refractive index)
The cured product of the present invention preferably has a high refractive index from the viewpoint of use for lenses and the like among optical component applications. The cured product of the present invention preferably has a refractive index nD at a wavelength of 589 nm of 1.45 or more, more preferably 1.50 or more, and particularly preferably 1.51 or more.

(Abbe number)
The cured product of the present invention preferably has a large Abbe number from the viewpoint of reducing chromatic aberration when used for lenses or the like among optical component applications. The cured product of the present invention preferably has an Abbe number of 45 or more at a wavelength of 589 nm, more preferably 50 or more, and particularly preferably 55 or more.
In this specification, the Abbe number νD is calculated by the following formula (A) by measuring the respective refractive indexes nD, nF, and nC at wavelengths 589 nm, 486 nm, and 656 nm.

(Water absorption rate)
The cured product of the present invention preferably has a low water absorption rate from the viewpoint of suppressing changes in optical properties (refractive index, Abbe number, and light transmittance) and dimensional change due to moisture absorption in the atmosphere. The cured product of the present invention preferably has a water absorption rate of 0.001 to 1.5%, more preferably 0.001 to 1.2%, and 0.001 to 1.0%. It is particularly preferred. In addition, the water absorption rate in the present invention is the weight immediately after production (Wi) and the weight (Wf) of the thermoset after being held for one week in an environmental test machine set at 85 ° C. and a relative humidity of 85%. It is the value obtained by the following formula.

(Thermal coloring)
From the viewpoint of using the cured product of the present invention for optical component applications, the thermal coloring is preferably -15% to 0%, more preferably -10% to 0%, and -5% to 0%. It is particularly preferred. In the thermal coloring in the present invention, the transmittance (T _before : unit%) of the cured product was measured with a spectrophotometer, and then the temperature was increased from room temperature to 270 ° C. at 2 ° C./min in a furnace under an N ₂ atmosphere. Thereafter, it was kept at 270 ° C. for 30 minutes. After cooling to 50 ° C., the sample was removed from the furnace, and the transmittance difference at 405 nm before and after the heat treatment in the furnace when the transmittance (T _after : unit%) was measured with a spectrophotometer is shown below. It is the value calculated from the formula of
Thermal coloring (%) = T _before -T _after

(Light transmittance)
The cured product of the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 75% or more, more preferably 80% or more, and 95% or more from the viewpoint of use in optical component applications. Particularly preferred. The light transmittance in terms of 1 mm thickness in the present invention is a value measured with a UV-visible absorption spectrum measuring device (UV-3100, manufactured by Shimadzu Corporation) by preparing a substrate having a thickness of 1.0 mm. is there.

(Tg)
The Tg of the cured product of the present invention is preferably 150 to 400 ° C, more preferably 180 to 300 ° C, and particularly preferably 240 to 300 ° C.

(size)
The cured product of the present invention preferably has a maximum thickness of 0.1 to 10 mm. The maximum thickness is more preferably 0.1 to 5 mm, and particularly preferably 0.15 to 3 mm. The cured product of the present invention preferably has a maximum diameter of 1 to 100 mm. The maximum diameter is more preferably 2 to 50 mm, and particularly preferably 2.5 to 10 mm. A cured product of such a size is particularly useful for optical parts having a high refractive index. Such a thick molded body is generally not easy because it is difficult to remove the solvent even if it is manufactured by the solution casting method, and it is not easy to mold it even if it is manufactured only by thermal polymerization. However, if the semi-cured material production method and the cured material production method of the present invention are used, the yield is high because molding is easy and burrs are not easily generated, and complex shapes such as aspherical surfaces can be easily realized. A cured product can be obtained. Thus, according to this invention, the hardened | cured material which has high heat resistance can be manufactured easily.

[Optical parts]
The cured product of the present invention is preferably a molded article having both high refraction, light transmittance and light weight and excellent optical properties, and the optical component of the present invention uses the cured product of the present invention. Features. The kind of the optical component of the present invention is not particularly limited. In particular, it can be suitably used as an optical component utilizing the excellent optical properties of the cured resin composition, particularly as an optical component that transmits light (so-called passive optical component). Examples of the optical functional device provided with such optical components include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, optical amplifier, etc.), camera, etc. And an imaging device such as a video.

  Examples of the passive optical component used in the optical functional device include a lens, a prism, a prism sheet, a panel (plate-shaped molded body), a film, an optical waveguide (film-like or fiber-like), an optical disk, and an LED seal. Examples thereof include a stopper. For such passive optical components, an optional coating layer, for example, a protective layer that prevents mechanical damage to the coated surface due to friction and wear, light rays with an undesirable wavelength that causes deterioration of inorganic particles and substrates, etc. A light absorbing layer that absorbs light, a transmission shielding layer that suppresses or prevents the transmission of reactive low molecules such as moisture and oxygen gas, an antiglare layer, an antireflection layer, a low refractive index layer, etc. A multilayer structure may be used. Specific examples of such an optional coating layer include a transparent conductive film and gas barrier film made of an inorganic oxide coating layer, a gas barrier film made of an organic coating layer, a hard coat, and the like. A known coating method such as a sputtering method, a dip coating method, or a spin coating method can be used.

The optical component using the cured product of the present invention is particularly suitable for a lens substrate. The lens substrate manufactured using the method for manufacturing a semi-cured product and the method for manufacturing a cured product of the present invention preferably has a high Abbe number, and has both high refraction, light transmittance, and light weight, and optical properties. Excellent characteristics. In addition, the refractive index of the lens substrate can be arbitrarily adjusted by appropriately adjusting the type of monomer constituting the cured resin composition.
In the present specification, the “lens substrate” means a single member that can exhibit a lens function. A film or a member can be provided on the surface or the periphery of the lens substrate according to the use environment or application of the lens. For example, a protective film, an antireflection film, a hard coat film, or the like can be formed on the surface of the lens substrate. Further, the periphery of the lens base material can be fitted and fixed to a base material holding frame or the like. However, these films and frames are members added to the lens base material, and are distinguished from the lens base material itself in this specification.

  When the lens substrate is used as a lens, the lens substrate itself may be used alone as a lens, or may be used as a lens with a film or a frame added as described above. The type and shape of the lens using the lens substrate are not particularly limited. The lens substrate is, for example, a spectacle lens, an optical device lens, an optoelectronic lens, a laser lens, a pickup lens, an in-vehicle camera lens, a portable camera lens, a digital camera lens, an OHP lens, or a microlens. Used in an array).

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

[Example 1]
<Obtaining vinyl polyfunctional monomers>
Vinyl polyfunctional monomers C-1, C-2, C-3, C-8, and C-9 were obtained by the following method.
C-1) NK Economer ML Shin-Nakamura Chemical Co., Ltd.
C-2) NK Economer AL Shin-Nakamura Chemical Co., Ltd.
C-3) Allyl methacrylate Tokyo Chemical Industry Co., Ltd.
C-8) TRIAM-501 Wako Pure Chemicals,
C-9) Tetraallyloxyethane Tokyo Chemical Industry.

<Preparation of cured resin composition>
57.3 parts by mass of the polyfunctional (meth) acrylic monomer Aa-1 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 24.4 parts by mass of the monofunctional (meth) acrylic monomer Ab-1 and the vinyl polyfunctional 17.2 parts by mass of monomer C-1 and 0.1 parts by mass of the following photo radical polymerization initiator F-1 (manufactured by BASF, Irgacure 184) and the following thermal radical polymerization initiator F-3 (manufactured by NOF Corporation) In addition, 1 part by mass of Perbutyl O) and 0.5 part by mass of the following thermal radical polymerization initiator F-4 (Nippon Yushi Co., Ltd., Park Mill H) were added to prepare a cured resin composition of Example 1.

  The structure of the polymerization initiator used is shown below. The following photo radical polymerization initiator F-2 is Irgacure 907 manufactured by BASF.

Thermal radical polymerization initiator

Photo radical polymerization initiator

<Evaluation after photopolymerization and / or thermal polymerization>
(Viscosity at 25 ° C. and 10 Hz after UV irradiation)
A cured resin composition injected into a mold having a diameter of 20 mm and a thickness of 1 mm was irradiated with ultraviolet light of 15 mW / cm ² using Execute 3000 (manufactured by HOYA Co., Ltd.) for the time shown in the following table, and a semi-cured product (photocured) Product).
Next, the value of the dynamic complex viscosity at 25 ° C. and 10 Hz was measured using a HAAKE Rheostress RS600, and the viscosity of the semi-cured product was obtained.

(Evaluation of mold resin clearance leakage (i))
A ceiling part of a thermoforming mold for lens production having a diameter of 4.0 mm consisting of an upper mold (ceiling part mold), a body mold, and a lower mold (bottom mold) was removed, and 10 mg of a cured resin composition was injected. The injected cured resin composition was irradiated with ultraviolet light of 15 mW / cm ² using Execute 3000 (manufactured by HOYA Co., Ltd.) for the time shown in the following table, and a semi-cured product whose viscosity was adjusted on a thermoforming mold. Produced. Next, the semi-cured product is sandwiched between the ceiling molds, and the entire semi-cured product is heated to 80 ° C. as it is and then heated to 200 ° C. while applying a pressure of 30 kgf / cm ² to the semi-cured product. After warming, it was cooled to room temperature.
In the process from injection of this cured resin composition into the thermoforming mold to cooling to room temperature, the resin leaked into the thermoforming mold clearance (the gap formed between the barrel mold and the upper and lower molds). The weight was measured and evaluated according to the following criteria.
A: The amount of resin leakage was less than 0.1 mg.
Δ: Resin leakage amount was 0.1 mg or more and less than 0.2 mg.
X: The amount of resin leakage is 0.2 mg or more, which is problematic in practical use.
The results obtained are listed in the table below.

(Evaluation of mold resin clearance leakage (ii))
The cured resin composition 10 mg injected into a cylindrical transparent preform mold having a diameter of 4 mm and a height of 1.5 mm is irradiated with 15 mW / cm ² ultraviolet rays using Execute 3000 (manufactured by HOYA). A semi-cured product was prepared by irradiation for the indicated time to adjust the viscosity. Subsequently, the semi-cured product in the shape of the preform mold was transferred from the preform mold to the thermoforming mold used in the mold resin clearance leakage evaluation (i) using air tweezers. After heating to 80 ° C., the temperature was raised to 200 ° C. while applying a pressure of 30 kgf / cm ² to the semi-cured product, and then cooled to room temperature.
In the process from transferring this semi-cured product to a thermoforming mold and cooling to room temperature, the length of burrs generated by resin leakage into the thermoforming mold clearance was measured and evaluated according to the following criteria: .
A: The amount of resin leakage was less than 0.1 mg.
Δ: Resin leakage amount was 0.1 mg or more and less than 0.2 mg.
X: The amount of resin leakage is 0.2 mg or more, which is problematic in practical use.
The results obtained are listed in the table below.
(Lens moldability evaluation)
The same process as the mold resin clearance leakage evaluation (ii) was repeated 10 times, and the appearance of each lens produced was evaluated using a digital micro scoop (trade name: VHX-1000) manufactured by Keyence Corporation.
Fine irregularities (wrinkles) on the surface of the flange portion of the lens or cracks in the lens were regarded as defective, and those not occurring were regarded as good. Ten lenses were evaluated, and the ratio of non-defective products was defined as the non-defective rate, and the following criteria were used.
A: The yield rate was 90% or more.
○: The yield rate was 80% or more.
Δ: The yield rate was 30% or more.
X: The yield rate was less than 30%.

(Refractive index / Abbe number)
The cured resin composition injected into a mold having a width of 8 mm, a length of 2.5 cm, and a thickness of 1 mm was irradiated with 15 mW / cm ² of ultraviolet light for the time described in the following table using Execute 3000 (manufactured by HOYA). A semi-cured product (photocured product) was obtained.
Next, the obtained semi-cured product was moved to the hot plate together with the mold, and heated at 200 ° C. for 5 minutes using the hot plate to obtain a thermo-cured product. The refractive index and Abbe number at 589 nm of the obtained thermoset were measured using an Abbe meter (manufactured by Atago Co., Ltd.), and the refractive index and Abbe number of the obtained cured product were obtained.
The results obtained are listed in the table below.

(Water absorption rate)
A cured resin composition injected into a mold having a diameter of 10 mm and a thickness of 1 mm was irradiated with ultraviolet light of 15 mW / cm ² using Execute 3000 (manufactured by HOYA Co., Ltd.) for the time shown in the following table, and a semi-cured product (photocured) Product).
Next, the semi-cured product was heated at 200 ° C. for 5 minutes using a hot plate to obtain a thermo-cured product, and the weight (Wi) was measured. Then, the weight (Wf) of the thermosetting material after hold | maintaining for one week in the environmental test machine set to 85 degreeC relative humidity 85% was measured. The water absorption of the obtained cured product was calculated from the following formula, and the obtained results are shown in the following table.

(Thermal coloring)
A cured resin composition injected into a mold having a diameter of 10 mm and a thickness of 1 mm was irradiated with ultraviolet light of 15 mW / cm ² using Execute 3000 (manufactured by HOYA Co., Ltd.) for the time shown in the following table, and a semi-cured product (photocured) Product).
Next, the semi-cured product was heated at 200 ° C. for 5 minutes using a hot plate to obtain a thermo-cured product. After measuring the transmittance (T _before : unit%) of this cured product with a spectrophotometer (manufactured by Shimadzu, UV-1650PC), the temperature was raised from room temperature to 270 ° C. at 2 ° C./min in a furnace under N ₂ atmosphere. Thereafter, it was kept at 270 ° C. for 30 minutes. After cooling to 50 ° C., the sample was taken out of the furnace, and the transmittance (T _after : unit%) was measured with a spectrophotometer (T% -after). The difference in transmittance at 405 nm of the sample before and after the heat treatment in the furnace was calculated from the following formula and expressed as thermal coloring.
Thermal coloring (%) = T _before -T _after

(270 ° C storage elastic modulus)
A cured resin composition injected into a mold having a diameter of 20 mm and a thickness of 0.2 mm was irradiated with ultraviolet rays of 15 mW / cm ² for a predetermined time using Execute 3000 (manufactured by HOYA Co., Ltd.), and a semi-cured product (photocured product) )
Next, the semi-cured product was heated at 200 ° C. for 5 minutes using a hot plate to obtain a thermo-cured product. The obtained thermosetting product was cut into a strip shape having a width of 5 mm, a length of 15 mm, and a thickness of 0.2 mm, and then a tensile mode using Rheogel-E4000 (manufactured by UBM Co., Ltd., dynamic viscoelasticity measuring device). The storage elastic modulus at 270 ° C. was measured under the conditions of a frequency of 10 Hz and a strain of 10 μm (constant) to obtain a 270 ° C. storage elastic modulus.
The results obtained are listed in the table below.

[Examples 2 to 22, Comparative Examples 1 to 6]
The used materials were changed as described in Table 1 and Table 2 below to prepare cured resin compositions, and semi-cured products and cured products of the Examples and Comparative Examples were produced and evaluated. The obtained results are shown in Table 1 or Table 2 below. The polyfunctional (meth) acrylic monomer Aa-2 is manufactured by Shin-Nakamura Chemical Co., Ltd., product name DCP, and Aa-10 is manufactured by Daicel Cytec Co., Ltd., product name PETIA (pentaerythritol triacrylate), which is non-conjugated. Polymers B-1, B-2 and B-6 each having a vinyl group in the side chain were each polymerized by the following method.

<Acquisition of polymer having non-conjugated vinyl group in side chain>
Polymers B-1, B-2, and B-6 having non-conjugated vinyl groups in the side chains used in Examples 12 to 22 were synthesized and obtained by the following method.

(Synthesis of B-1)
Reflux condenser, 1L three-necked flask equipped with a gas introduction cock, tricyclo [5,2,1,0 ^2,6] dec-8-yl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name FA-513AS) 20. 0 g, allyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 30.0 g, ethyl acetate 50.0 g, and after nitrogen substitution twice, V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. as an initiator After adding 0.6 g and replacing with nitrogen twice, the mixture was heated at 65 ° C. for 6 hours under a nitrogen stream. Thereafter, the reaction solution was poured into 2 L of methanol, and the precipitated white solid was collected by suction filtration. After drying under reduced pressure at 70 ° C. for 5 hours and distilling off the solvent, a polymer B-1 was obtained (yield 60%, number average molecular weight 24,000, weight average molecular weight 58,000).

(Synthesis of B-2)
A 1 L three-necked flask equipped with a gas introduction cock was charged with 50.0 g of 1,2-epoxy-4-vinylcyclohexane (manufactured by Daicel Chemical Industries, Celoxide 2000) and 490.0 g of dehydrated toluene, and sufficiently substituted with nitrogen. Thereafter, the liquid temperature was adjusted to −70 ° C., and then a solution composed of 1.0 g of boron trifluoride diethyl ether complex and 9.0 g of dehydrated toluene was dropped over about 1 hour to carry out the reaction. After completion of dropping, the reaction was further continued for 1 hour. Thereafter, the reaction solution was poured into 2 L of methanol, and the precipitated white solid was collected by suction filtration. The polymer B-2 was obtained by drying under reduced pressure at 60 ° C. for 5 hours and removing the solvent (yield 50%, number average molecular weight 3,100, weight average molecular weight 18,100).

(Synthesis of B-6)
After adding 15.0 g of allyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 15.0 g of 2-norbornene, and 170 g of toluene to a 500 mL three-necked flask equipped with a reflux condenser and a gas introduction cock, and substituting with nitrogen twice, After adding 0.9 g of V-601 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. as an initiator, and after substituting with nitrogen twice, the mixture was heated at 90 ° C. for 4 hours under a nitrogen stream, and then heated at 100 ° C. for 1 hour. did. Thereafter, the reaction solution was poured into 1.5 L of methanol, and the precipitated white solid was collected by suction filtration. It dried under reduced pressure at 40 degreeC for 2 hours, and polymer B-6 was obtained by distilling a solvent off (yield 30%, number average molecular weight 20,000, weight average molecular weight 70,000).

From Tables 1 to 3, the semi-cured product obtained by the production method of the present invention has a complex viscosity controlled within the range defined by the production method of the present invention. It was found that the cured product of the present invention obtained by performing the above-described method suppresses the generation of burrs during molding, has a high yield rate after molding, and has high heat resistance at 270 ° C.
On the other hand, from Comparative Example 1, when the complex viscosity of the semi-cured product is lower than the lower limit specified in the present invention, the occurrence of burrs during molding is large when the thermal polymerization step is performed thereafter, and the yield rate after molding is low. I understood it. From Comparative Example 2, it was found that when the complex viscosity of the semi-cured product exceeded the upper limit specified in the present invention, the yield rate after molding was low when the thermal polymerization step was performed thereafter. From Comparative Examples 3 to 6, when the complex viscosity of the semi-cured product is controlled so as to be out of the range specified by the production method of the present invention without adding a vinyl-based polyfunctional monomer, the thermal polymerization step is performed thereafter. It was found that the yield rate after molding was low. In particular, when a vinyl group-containing polyfunctional monomer is not added, it is difficult to control by jumping from the lower limit of the required viscosity specified in the production method of the present invention to the upper limit at a stretch with a slight change in time. It was found that the yield rate after molding was low).
Further, from Examples 19 and 20, when the polymer having a non-conjugated vinyl group in the side chain is below the lower limit of the preferred range defined in the present invention, the mold resin clearance leakage (i) is insufficient, On the other hand, when the polymer having a non-conjugated vinyl group in the side chain exceeds the upper limit value of the preferred range defined in the present invention, it is found that the initial viscosity becomes too high and dispensing before molding becomes difficult. It was. Further, comparing Examples 12 to 18 with other examples, when the cured resin composition of the present invention to which a polymer having a conjugated vinyl group in the side chain was used, the directly cured resin composition was used for thermoforming. It was found that resin leakage to the mold clearance when injected into the mold can also be suppressed. From Examples 21 and 22, when the content of the vinyl group-containing polyfunctional monomer relative to the (meth) acrylic monomer is 42% by mass exceeding the optimum range defined in the present invention, the storage elastic modulus (heat resistance) at 270 ° C. is Δ It turns out that it becomes evaluation, and when the content of the vinyl group-containing polyfunctional monomer with respect to the (meth) acrylic monomer is 6.4% by mass below the optimum range specified in the present invention, the lens moldability evaluation may be Δ evaluation. all right. In Examples 15 and 16 in which the vinyl group-containing polyfunctional monomer is different from the general formula (2), it was found that although the moldability was good, the lens characteristics were somewhat inferior.

(Light transmittance)
About the hardened | cured material of each Example manufactured similarly to evaluation of a 270 degreeC storage elastic modulus, the light transmittance was measured by the method as described in this specification. As a result, all the cured products had a light transmittance of 95% or more.

Claims (20)

Monomer having two or more radical polymerizable groups and containing non-conjugated vinyl group, non-conjugated (meth) allyl group or non-conjugated isopropenyl group, (meth) acrylate monomer, photo radical polymerization initiator and thermal radical polymerization initiation Irradiating the cured resin composition containing the agent with light to obtain a semi-cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz;
A method of producing a cured product comprising a semi-cured product placed in a mold, subjected to pressure deformation, and heated to thermally polymerize to obtain a cured product (however, the (meth) acrylate monomer includes 2 It does not include those corresponding to monomers having one or more radically polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl group). The monomer having the two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl group is represented by the following general formula (1). A method for producing a cured product.

(In general formula (1), R ¹ represents a functional group containing a radical polymerizable group, R ² represents a single bond or a (n + 1) -valent saturated linking group, and n represents an integer of 1 to 8). The method for producing a cured product according to claim 2, wherein R ^{1 in the} general formula (1) is a (meth) acryloyloxy group or a vinyl group. The cured product according to claim 2 or 3, wherein R ^{2 in the} general formula (1) is a linking group composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. Method.   N of the said General formula (1) is an integer of 1-4, The manufacturing method of the hardened | cured material as described in any one of Claims 2-4. The monomer having the two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl group is represented by the following general formula (2). A method for producing a cured product.

(In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a single bond or a saturated hydrocarbon linking group having 1 to 10 carbon atoms)   The said (meth) acrylate monomer is a polyfunctional (meth) acrylate monomer, or is a mixture of a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate monomer. The manufacturing method of hardened | cured material as described in any one of.   The manufacturing method of the hardened | cured material as described in any one of Claims 1-7 in which the said (meth) acrylate monomer contains the (meth) acrylate monomer which has alicyclic structure.   A monomer in which the cured resin composition has the two or more radical polymerizable groups with respect to the cured resin composition and includes a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl group. The manufacturing method of the hardened | cured material as described in any one of Claims 1-8 containing 0.5-35 weight%.   The (meth) acrylate monomer is composed of a polyfunctional (meth) acrylate monomer and a monofunctional (meth) acrylate monomer, and the total amount of the polyfunctional (meth) acrylate monomer and the monofunctional (meth) acrylate monomer is The manufacturing method of the hardened | cured material as described in any one of Claims 1-9 which contains a polyfunctional (meth) acrylate monomer 30 to 90 weight%.   Furthermore, the manufacturing method of the hardened | cured material as described in any one of Claims 1-10 containing the polymer which has a nonconjugated vinyl group in a side chain.   The manufacturing method of the hardened | cured material of Claim 11 which contains 5-50 mass% of polymers which have a nonconjugated vinyl group in a side chain with respect to the total amount of the said cured resin composition.   Hardened | cured material manufactured by the manufacturing method of the hardened | cured material as described in any one of Claims 1-12.   The cured product according to claim 13, wherein the cured product has a refractive index of 1.45 or more at a wavelength of 589 nm, an Abbe number of 45 or more, and a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 75% or more. object.   The optical component using the hardened | cured material of Claim 13 or 14.   A monomer having two or more radical polymerizable groups, a monomer containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl group, a (meth) acrylate monomer, a non-conjugated vinyl group in the side chain. A cured resin composition containing a polymer, a photo radical polymerization initiator and a thermal radical polymerization initiator (however, the (meth) acrylate monomer has two or more radical polymerizable groups, a non-conjugated vinyl group, a non-conjugated vinyl group, (Does not include those corresponding to monomers containing a conjugated (meth) allyl group or a non-conjugated isopropenyl group). The monomer having two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group, or a non-conjugated isopropenyl group is represented by the following general formula (2). Cured resin composition.

(In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a single bond or a saturated hydrocarbon linking group having 1 to 10 carbon atoms) Monomer having two or more radical polymerizable groups and containing non-conjugated vinyl group, non-conjugated (meth) allyl group or non-conjugated isopropenyl group, (meth) acrylate monomer, photo radical polymerization initiator and thermal radical polymerization initiation The cured resin composition containing an agent is irradiated with light, and the complex viscosity at 25 ° C. and a frequency of 10 Hz is 10 ⁵ to 10 ⁸ mPa ·. a process for producing a semi-cured product of s (wherein the (meth) acrylate monomer has two or more radical polymerizable groups, and is a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl) It does not include those corresponding to monomers containing groups).   A semi-cured product produced by the method for producing a semi-cured product according to claim 18. Cured resin having two or more radical polymerizable groups and containing a non-conjugated vinyl group, a non-conjugated (meth) allyl group or a non-conjugated isopropenyl group, a (meth) acrylate monomer, and a photo radical polymerization initiator A method of forming a semi-cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz by irradiating the composition with light (provided that the (meth) acrylate monomer has two or more And a monomer having a non-conjugated vinyl group, non-conjugated (meth) allyl group, or non-conjugated isopropenyl group).