WO2013047223A1 - Curable composition - Google Patents

Abstract

The present invention relates to: a curable composition which contains (A) an allyl group-terminated allyl ester oligomer which has three or more terminal allyl groups, (B) a flexible allyl group-terminated allyl ester oligomer which contains, as the main skeleton, a structural unit containing a carbonate bond and which has a number average molecular weight of 500-50,000, (C) a polyfunctional (meth)acrylic compound and (D) a polymerization initiator; a transparent optical material which is obtained by polymerizing and curing the curable composition by applying light and/or heat to the curable composition, said transparent optical material having excellent flexibility, heat resistance, transparency and surface hardness; and an optical film, an optical sheet, an optical waveguide, an optical lens, an optical sealing agent, an optical adhesive and a light guide plate, each of which uses the optical material.

Description

Curable composition

The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition from which an optical resin film or sheet having high flexibility and excellent heat resistance, transparency, and surface hardness can be obtained by curing.

Conventionally, cured products obtained by polymerizing and curing polyvalent allyl ester compounds having a plurality of allyl ester groups in the molecule are excellent in transparency, heat resistance, electrical properties, and light resistance, and are optical materials, electronic equipment, artificial marble. , Decorative plates, unsaturated polyester resin crack prevention materials, and the like. For example, Patent Document 1 (International Publication No. 02/33447 pamphlet (EP1331494） A1)) and Patent Document 2 (Japanese Patent Laid-Open No. 2009-197102 (US2009 / 209718 A1)) describe an optical lens using a polyvalent allyl ester compound. However, in Patent Document 3 (Japanese Patent Laid-Open No. 2011-22490) and Patent Document 4 (Japanese Patent Laid-Open No. 2008-44357 (WO2008 / 010588 A1)), a substrate using a polyvalent allyl ester compound is disclosed in Patent Document 5 ( Japanese Laid-Open Patent Publication No. 2010-84008) discloses a semiconductor device using a polyvalent allyl ester compound.

In recent years, electronic devices represented by mobile phones and flat-screen TVs have a strong need for higher functionality, smaller size, thinner thickness, and lighter weight, and the optical members used for them have been replaced by glass members instead of resin members. Is being considered. Resins used as glass substitutes are required to have heat resistance and transparency that are closer to glass, and lighter and more difficult to break than glass.

Examples of resins that have been used as glass substitutes include polycarbonate (PC) and polyethylene terephthalate (PET) from the viewpoint of having good mechanical strength and excellent transparency, and each has a glass transition temperature of 70. The temperature is about 140 ° C. and the heat resistance is not sufficient, and the usage is limited.

A cured product obtained by polymerizing and curing a polyvalent allyl ester compound has higher heat resistance and transparency than polycarbonate (PC) and polyethylene terephthalate (PET), but has sufficient flexibility depending on the application. In addition to transparency and heat resistance, moderate flexibility is strongly desired.

As a method for improving the flexibility of a thermosetting resin, introduction of a highly flexible skeleton represented by a polyether skeleton into a molecular chain (for example, Patent Document 6: JP-A-2007-138002), core shell Addition of a rubber-like rubber (for example, Patent Document 7: JP 2011-57734 A) and introduction of a thermoplastic resin (for example, Patent Document 8: JP 2010-202862 A) have been performed. There have been problems such as a decrease in light resistance and transparency, and a decrease in handling properties due to an increase in viscosity.

International Publication No. 02/33447 Pamphlet JP 2009-197102 A JP 2011-22490 A JP 2008-44357 A JP 2010-84008 A JP 2007-138002 A JP 2011-57734 A JP 2010-202862 A

An object of the present invention is to provide a curable composition suitable for the production of a film or sheet having transparency required for optical applications, high flexibility, excellent heat resistance, handling properties, and high surface hardness. It is what.

The inventors of the present invention have completed the present invention as a result of intensive studies in order to achieve the above object.
That is, the present invention provides the following curable compositions [1] to [12], an optical material [13], an optical film [14], an optical sheet, an optical waveguide, an optical lens, an optical sealant, The present invention relates to an optical adhesive or a light guide plate.
[1] (A) General formula (1)

(Wherein X ¹ represents an organic residue derived from a divalent carboxylic acid or carboxylic acid anhydride having an alicyclic structure) and has at least three end groups represented by the general formula ( 2)

(In the formula, X ² represents an organic residue derived from a divalent carboxylic acid or carboxylic anhydride having an alicyclic structure, and Y ¹ has 2 to 20 carbon atoms having 3 to 6 hydroxyl groups. Represents an organic residue derived from a polyhydric alcohol, wherein Y ¹ represents an ester bond, a group represented by the above general formula (1) as a terminal group, and a structural unit represented by the above general formula (2). An allyl group-terminated allyl ester oligomer having a structure represented by:
(B) General formula (3)

(Wherein X ³ represents an optionally substituted cycloalkylene group having 5 to 10 carbon atoms or an optionally substituted alkylene group having 2 to 10 carbon atoms) and formula (4)

As well as the end group represented by formula (5)

(Wherein R ¹ and R ² each independently represents an alkylene group having 2 to 20 carbon atoms which may have an alkyl branch, and X ⁴ may have a substituent having 5 to 10 carbon atoms) A cycloalkylene group or an alkylene group having 2 to 10 carbon atoms which may have a substituent, and n and m represent any natural number.)
An allyl group-terminated allyl ester oligomer having a structure represented by the formula:
A curable composition comprising (C) a polyfunctional (meth) acrylic compound; and (D) a polymerization initiator.
[2] The allyl group-terminated allyl ester oligomer (B) is further represented by the general formula (6)

(Wherein R ³ represents an alkylene group having 2 to 20 carbon atoms which may have an alkyl branch, and X ⁵ represents a cycloalkylene group or substituent having 5 to 10 carbon atoms which may have a substituent. Represents an optionally substituted alkylene group having 2 to 10 carbon atoms, and q represents an arbitrary natural number.)
2. The curable composition according to item 1, which has a structure represented by:
[3] 1 to 40 parts by mass of the allyl group-terminated allyl ester oligomer (B) and 5 to 60 parts by mass of the polyfunctional (meth) acrylic compound (C) with respect to 100 parts by mass of the allyl group-terminated allyl ester oligomer (A). 1 or 2 containing 0.1 to 10 parts by mass of a photopolymerization initiator (D1) as a polymerization initiator (D) and 0.1 to 10 parts by mass of a thermal polymerization initiator (D2) as a polymerization initiator (D) The curable composition according to 1.
[4] X ¹ and X ^{2 in the} general formulas (1) and (2) may each independently have a substituent, 1,2-cyclohexylene group, 1,3-cyclohexane 4. The curable composition according to any one of items 1 to 3, which is a xylene group, 1,4-cyclohexylene group, or norbornylene group.
[5] In any one of the above items 1 to 4, wherein Y ¹ in the general formula (2) is an organic residue derived from a polyhydric alcohol having 3 to 4 hydroxyl groups and having 5 to 10 carbon atoms The curable composition as described.
[6] The allyl group-terminated allyl ester oligomer (A) is represented by the following formula:

(Wherein r represents an arbitrary natural number), or

(In the formula, s represents an arbitrary natural number.)
6. The curable composition according to any one of 1 to 5 above,
[7] X ³ , X ⁴ and X ^{5 in the} general formulas (3), (5) and (6) are each independently 1,2-cyclohexylene group or 1,3-cyclohexylene group 7. The curable composition according to any one of 1 to 6 above, which is 1,4-cyclohexylene group or norbornylene group.
[8] Any one of [1] to [7], wherein at least one of R ¹ , R ² and R ^{3 in} the general formulas (5) and (6) is an alkylene group having an alkyl branch having 1 to 4 carbon atoms. Curable composition.
[9] The curable composition as described in any one of 1 to 8 above, wherein R ¹ and R ² in the general formula (5) are 1,6-hexylene group or 2-methyl-1,5-pentylene group. .
[10] The curable composition as described in any one of 1 to 8 above, wherein R ¹ and R ² in the general formula (5) are nonylene groups.
[11] In the allyl group-terminated allyl ester oligomer (B), R ¹ represents R ⁴ , R ² represents R ⁵ , and X ³ and X ⁴ are 1,4-cyclohexylene groups (7) )

(In the formula, R ⁴ and R ⁵ each independently represents a 1,6-hexylene group or a 2-methyl-1,5-pentylene group, and n and m represent an arbitrary natural number.)
11. The curable composition according to any one of items 1 to 10, which is an oligomeric compound represented by
[12] Any one of [1] to [11] above, wherein the polyfunctional (meth) acrylic compound (C) is mainly composed of a (meth) acrylate monomer or oligomer having three or more (meth) acryloyloxy groups. The curable composition as described.
[13] An optical material obtained by curing the curable composition as described in any one of 1 to 12 above by applying light and / or heat.
[14] An optical film, an optical sheet, an optical waveguide, an optical lens, an optical sealant, an optical adhesive, or a light guide plate using the optical material according to item 13 above.

By polymerizing and curing the curable composition of the present invention, a transparent resin film or sheet material suitable for optical applications having high flexibility, excellent heat resistance, handling properties, and high surface hardness can be obtained.

Hereinafter, the present invention will be described in detail.
The curable composition of the present invention is characterized by including the following components (A) to (D).

(A) Allyl group-terminated allyl ester oligomer:
The main component of the curable composition of the present invention, having three or more terminal groups represented by the following general formula (1), and having a structure represented by the following general formula (2) It is a component that contributes to the development of heat resistance.

In the formula, X ¹ represents an organic residue derived from a divalent carboxylic acid or carboxylic anhydride having an alicyclic structure.

In the formula, X ² represents an organic residue derived from a divalent carboxylic acid or carboxylic anhydride having an alicyclic structure. Y ¹ represents an organic residue derived from a polyhydric alcohol having 2 to 20 carbon atoms and having 3 to 6 hydroxyl groups. However, Y ¹ may have a branched structure having a structural unit represented by the above general formula (2) by an ester bond and having a group represented by the above general formula (1) as a terminal group.

X ¹ and X ² in the general formulas (1) and (2) represent an organic residue derived from a divalent carboxylic acid or carboxylic anhydride having an alicyclic structure. As specific examples, 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1, 4-cyclohexylene, methylcyclohexylene, dimethylcyclohexylene, cycloheptylene, 1-ethylcyclopentylene, cyclooctylene, cyclononylene, cyclodecylene, bicyclodecylene, norbornylene and cyclohexanedi A methylene group etc. are mentioned.

Among these, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene which may have a substituent may be obtained because a cured product having excellent heat resistance can be obtained. Group, norbornylene group and bicyclodecylene group are preferable, and the radical polymerizable compound has relatively low viscosity and high handling property, and therefore may have a substituent, 1,2-cyclohexylene group, 1, More preferred are 3-cyclohexylene group, 1,4-cyclohexylene group and norbornylene group. X ¹ and X ² may be the same or different. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms.

Y ¹ in the general formula (2) represents an organic residue derived from a polyhydric alcohol having 2 to 20 carbon atoms and having 3 to 6 hydroxyl groups. Specific examples include 1-methylethylene group, 2-methylethylene group, 1-methyl-propylene group, 2-methyl-propylene group, 2-ethyl-3-propylpropylene group, 2-ethyl-2-butylpropylene group. 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 2,4-dimethylpentylene group, 1-methyloctylene group, 2-methyloctylene group, 2-methyl-2 -Methylenepropylene group, 2-ethyl-2-methylenepropylene group, 2,2-dimethylenepropylene group and the like. When the number of hydroxyl groups is 2 or less, heat resistance and surface hardness are lowered. When the number of hydroxyl groups is 7 or more, gelation may occur when the allyl group-terminated allyl ester oligomer is synthesized, or the viscosity of the oligomer may become too high.

Among these, organic residues derived from polyhydric alcohols having 3 or 4 hydroxyl groups and 5 to 10 carbon atoms are preferable, and organic residues derived from trimethylolpropane and pentaerythritol are more preferable. When the number of hydroxyl groups is 5 or more, gelation tends to occur during oligomer synthesis. In addition, some hydroxyl groups of the polyhydric alcohol may remain as hydroxyl groups without ester bonding.

At least one structural unit represented by the general formula (2) is required in the (A) allyl group-terminated allyl ester oligomer, but since an appropriate viscosity is obtained, workability is improved and toughness of the cured product is obtained. Therefore, it is better to repeat this structure to increase the molecular weight of the whole (A) allyl group-terminated allyl ester oligomer to some extent. However, if the molecular weight becomes too large, the molecular weight between cross-linking points becomes excessively large, the glass transition temperature (Tg) is lowered, and the heat resistance is lowered. Therefore, the number average molecular weight of the allyl ester oligomer of component (A) is preferably 500 to 50,000, and more preferably 800 to 10,000.

In the allyl group-terminated allyl ester oligomer (A) having the structure represented by the general formulas (1) and (2), one type of compound may be used alone, or two or more types may be used in combination. . Specific examples of the allyl group-terminated allyl ester oligomer (A) include those represented by the following formulae.

In the formula, r represents an arbitrary natural number.

In the formula, s represents an arbitrary natural number.

An allyl group-terminated allyl ester oligomer (A) having an allyl group and an ester structure is (1) an esterification reaction between a compound containing an allyl group and a hydroxyl group (hereinafter collectively referred to as allyl alcohol) and a compound containing a carboxyl group, It can be obtained by (2) an esterification reaction between a compound containing an allyl group and a carboxyl group and a compound containing a hydroxyl group, or (3) an ester exchange reaction between an ester compound consisting of allyl alcohol and dicarboxylic acid and a polyhydric alcohol.

(B) Allyl group terminal allyl ester oligomer:
It is a characteristic component in the curable composition of the present invention, contains a terminal group represented by the following general formulas (3) and (4), and a structure represented by the following general formula (5), This component contributes to the development of the flexibility of the cured product having an average molecular weight of 500 to 50,000.

In the formula, X ³ represents an optionally substituted cycloalkylene group having 5 to 10 carbon atoms or an optionally substituted alkylene group having 2 to 10 carbon atoms.

In the formula, each of R ¹ and R ² independently represents an alkylene group having 2 to 20 carbon atoms which may have an alkyl branch, and X ⁴ has 5 to 10 carbon atoms which may have a substituent. It represents a cycloalkylene group or an alkylene group having 2 to 10 carbon atoms which may have a substituent, and n and m represent any natural number.

Moreover, the allyl group terminal allyl ester oligomer (B) may further have a structure represented by the general formula (6).

In the formula, R ³ represents an alkylene group having 2 to 20 carbon atoms which may have an alkyl branch, and X ⁵ represents a cycloalkylene group or substituent having 5 to 10 carbon atoms which may have a substituent. Represents an alkylene group having 2 to 10 carbon atoms which may be present, and q represents an arbitrary natural number.

The number average molecular weight of the allyl group-terminated allyl ester oligomer (B) is from 500 to 50,000, more preferably from 1,000 to 10,000, and even more preferably from 1,500 to 5,000. The number average molecular weight is a molecular weight in terms of polystyrene measured by GPC. When the number average molecular weight is less than 500, the effect of imparting flexibility may be lowered. If it exceeds 50,000, the viscosity of the allyl group-terminated allyl ester oligomer (B) increases and the handling property decreases. In addition, the compatibility with the polyvalent allyl ester compound is reduced, and the cured product may be whitened.

N and m in the general formula (5) are arbitrary natural numbers. As described above, the number average molecular weight of the allyl group-terminated allyl ester oligomer (B) has a distribution of 500 to 50,000. The values of n and m indicate the number of repetitions that is the number average molecular weight. Therefore, the values of n and m cannot be uniquely determined, but n is 1 to 500 and m is 1 to 180. More preferably, n is 1 to 300, m is 1 to 120, more preferably n is 1 to 150, and m is 1 to 100.

Q in the general formula (6) is an arbitrary natural number. Although it cannot be uniquely determined for the same reason as in the case of n and m, q is 1 to 500. More preferably, it is 1 to 120, and further preferably 1 to 100.

X ³ , X ⁴ and X ⁵ in the general formulas (3), (5) and (6) may have a cycloalkylene group having 5 to 10 carbon atoms or a substituent which may have a substituent. An alkylene group having 2 to 10 carbon atoms. X ³ , X ⁴ and X ⁵ are preferably the same, but may be different.
Method for producing allyl terminal allyl ester oligomer (B) will be described later, using a dicarboxylic acid diallyl ester containing the structure of X ^3, X ⁴ and X ⁵ as part of the raw materials. If one type of dicarboxylic acid diallyl ester is used as a raw material, X ³ , X ⁴ and X ⁵ are the same, and if different types of dicarboxylic acid diallyl ester are used, X ³ , X ⁴ and X ⁵ may be different. There are also X ⁴ is different for each unit structure of Formula (5) where m pieces present in the allyl group-terminated allyl ester oligomer (B).

The cycloalkylene group having 5 to 10 carbon atoms which may have a substituent represented by X ³ , X ⁴ and X ⁵ is a cyclohexane group having 6 to 8 carbon atoms from the viewpoint of achieving both heat resistance, transparency and handling properties. An alkylene group is preferred. The cycloalkylene group having 5 to 10 carbon atoms may have a single ring or a plurality of ring structures such as a bicycloalkylene group.
The cycloalkylene group having 5 to 10 carbon atoms is preferably a cyclohexylene group, a norbornylene group or a bicyclodecylene group from the viewpoint of heat resistance.
Examples of the substituent for the cycloalkylene group having 5 to 10 carbon atoms include alkyl groups such as a methyl group and an ethyl group.

Specific examples of the cycloalkylene group having 5 to 10 carbon atoms which may have a substituent include 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1 , 3-cyclohexylene group, 1,4-cyclohexylene group, methylcyclohexylene group, dimethylcyclohexylene group, cycloheptylene group, 1-ethylcyclopentylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, Bicyclodecylene group, norbornylene group, and cyclohexanedimethylene group can be mentioned. Among these, since a cured product having excellent heat resistance can be obtained, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, norbornylene group, bicyclodecylene group The allyl group-terminated allyl ester oligomer (B) has a relatively low viscosity and high handling properties, so that 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4- A cyclohexylene group and a norbornylene group are more preferable.

The alkylene group having 2 to 10 carbon atoms which may have a substituent represented by X ³ , X ⁴ and X ⁵ is preferably an alkylene group having 2 to 8 carbon atoms from the viewpoint of versatility.
Examples of the substituent of the alkylene group having 2 to 10 carbon atoms include alkyl groups such as a methyl group and an ethyl group.

Specific examples of the alkylene group having 2 to 10 carbon atoms which may have a substituent include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group and decylene group. Among them, from the viewpoint of versatility, an ethylene group, a propylene group, a butylene group, and an octylene group are preferable.

R ¹ and R ² in the general formula (5) each independently represent an alkylene group having 2 to 20 carbon atoms which may have an alkyl branch.
R ¹ and R ² in the general formula (5) are derived from carbonate diol which is one of the raw materials of the allyl group terminal allyl ester oligomer (B). N R ¹ present in the general formula (5) may be the same or different. If alkylene groups corresponding to R ¹ and R ² of the starting carbonate diol are plural kinds (copolymerization type), plural kinds of R ¹ are also present.

The alkylene group having 2 to 20 carbon atoms which may have an alkyl branch is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of achieving both flexibility and handleability of the cured product, and alkylene having 4 to 9 carbon atoms. Groups are more preferred. The alkyl branch is preferably an alkyl group having 1 to 3 carbon atoms. There may be two or more alkyl branches.

Examples of the alkylene group represented by R ¹ and R ² include those having a linear or branched skeleton.
Specific examples of the linear alkylene group include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group, and among them, a butylene group and a hexylene group. A nonylene group is preferred.

Specific examples of the alkylene group having a branched skeleton, that is, the alkylene group having 2 to 20 carbon atoms having an alkyl branch include 1-methylethylene group, 2-methylethylene group, 1-methyl-propylene group, 2-methyl-propylene. Group, 2-ethyl-3-propylpropylene group, 2-ethyl-2-butylpropylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 2,4-dimethylpentylene Group, 1-methyloctylene group, 2-methyloctylene group, 2-methyl-2-methylenepropylene group, 2-ethyl-2-methylenepropylene group, 2,2-dimethylenepropylene group and the like.

R ³ representing an alkylene group having 2 to 20 carbon atoms which may have an alkyl branch in the general formula (6) is derived from an alkylene diol which is an arbitrary raw material of the allyl group-terminated allyl ester oligomer (B). Specific examples thereof are the same as those of the alkylene group having 2 to 20 carbon atoms represented by R ¹ and R ² described above.

Furthermore, it is more preferable that at least one of R ¹ , R ² and R ³ is a branched alkylene group. By having branching, the crystallinity of the allyl group-terminated allyl ester oligomer (B) can be suppressed, the viscosity and the melting point can be lowered, and the handling property of the radical polymerizable compound can be improved. Among the branched alkylene groups, 2-methyl-propylene group, 2-ethyl-2-butylpropylene group, 2-methylpentylene group, 3-methylpentylene group, and 2,4-dimethylpentylene are particularly preferable. A 2-methyloctylene group.

The ratio of the alkylene group having a branch in the total amount of alkylene groups of R ¹ , R ² and R ^{3 in} the allyl group terminal allyl ester oligomer (B) is preferably 10 mol% or more, more preferably 30 mol% or more.

When X ³ and X ⁴ are 1,4-cyclohexylene groups and R ¹ , R ² and R ³ are hexylene groups or 2-methylpentylene groups, the allyl group-terminated allyl ester oligomer (B) of the present invention is generally Formula (7)

In the formula, R ⁴ and R ⁵ each independently represents a 1,6-hexylene group or a 2-methyl-1,5-pentylene group, and n and m represent any natural number.
Indicated by

When X ³ and X ⁴ are 1,4-cyclohexylene groups and R ¹ , R ² and R ³ are nonylene groups which may have an alkyl branch, the allyl group-terminated allyl ester oligomer (B) of the present invention is It is shown by the following general formula.

In the formula, R ⁶ and R ⁷ each independently represent — (CH ₂ ) ₉ — or — (CH) ₂ CH (CH ₃ ) (CH ₂ ) ₆ —, and n and m represent any natural number.

As the allyl group-terminated allyl ester oligomer (B), one type of compound may be used alone, or two or more types may be used in combination. The allyl group terminal allyl ester oligomer (B) is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the allyl group terminal allyl ester oligomer (A). If the amount of the allyl group terminal allyl ester oligomer (B) is too small, the flexibility is inferior, and if it is too large, the heat resistance may be lowered.

The allyl group-terminated allyl ester oligomer (B) can be produced by distilling off allyl alcohol produced as a by-product while conducting a transesterification reaction between the compound of the general formula (8) and polycarbonate diol in the presence of a catalyst. .

In the formula, X ⁶ represents an optionally substituted cycloalkylene group having 5 to 10 carbon atoms or an optionally substituted alkylene group having 2 to 10 carbon atoms.

Examples of the cycloalkylene group having 5 to 10 carbon atoms which may have a substituent represented by X ⁶ or the alkylene group having 2 to 10 carbon atoms which may have a substituent include X ³ , X ⁴ and X ^5. And the same group as the cycloalkylene group having 5 to 10 carbon atoms which may have a substituent or an alkylene group having 2 to 10 carbon atoms which may have a substituent. ), (5) and (6) may be selected appropriately in accordance with the structure shown. X ⁶ is not limited to one type, and a plurality of types of compounds represented by the general formula (8) can be used.

Specific examples of the compound represented by the general formula (8) include diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, diallyl endomethylenetetrahydrophthalate, methyl Examples include diallyl tetrahydrophthalate, diallyl decahydronaphthalenedicarboxylate, diallyl 5-norbornene 2,3-dicarboxylate, diallyl adipate, diallyl succinate, diallyl maleate, and the like. These compounds can be used in combination of two or more as required. Moreover, it is not limited to the above-mentioned specific example.

The polycarbonate diol used for the production of the allyl group-terminated allyl ester oligomer (B) is represented by the general formula (9).

In the formula, R ¹ and R ² each independently represents an alkylene group having 2 to 20 carbon atoms, as in the case of the general formula (5).

As described above, in the allyl group-terminated allyl ester oligomer (B), it is more preferable that at least one of R ¹ and R ² is a branched alkylene group. Among the alkylene groups having a branch, those having no branch at the terminal carbon are particularly preferable. Polycarbonate diol derived from an alkylene group having no branch at the end is preferable from the viewpoint of productivity because the hydroxyl groups in the molecule are all primary hydroxyl groups and the reaction rate of the transesterification reaction is fast. When the substituent is present at the terminal, the reaction rate is lowered, and the productivity is lowered. Specific examples of the alkylene group having no branch at the terminal carbon include 2-methyl-propylene group, 2-ethyl-2-butylpropylene group, 2-methylpentylene group, 3-methylpentylene group, 2,4 -A dimethylpentylene group, a 2-methyloctylene group and the like.

Polycarbonate diols can be used in combination of two or more as required. Moreover, it is not limited to the above-mentioned specific example.

The polycarbonate diol used in the reaction is generally a condensate produced by a transesterification reaction between a diol compound such as dimethyl carbonate, diphenyl carbonate or ethylene carbonate and a diol, and is an aggregate of oligomers having different molecular weights. Have a distribution.

The number average molecular weight of the polycarbonate diol for the radical polymerizable compound of the present invention is preferably 300 to 10,000, and more preferably 500 to 3,000. When the average molecular weight is small, various properties such as heat resistance and toughness derived from the polycarbonate skeleton are hardly expressed. When the average molecular weight is large, the polycarbonate diol becomes a solid and the workability is lowered, for example, heating is required during use. Moreover, when the allyl group terminal allyl ester oligomer (B) synthesize | combined using it and an allyl group terminal allyl ester oligomer (A) are hardened, problems, such as whitening of hardened | cured material, may arise.

When the allyl group-terminated allyl ester oligomer (B) has a structure represented by the general formula (6), an alkylene diol can be used together with a polycarbonate diol as the diol. Specific examples of the alkylene diol include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3 -Butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- Examples include hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, and 1,9-nonanediol.

The molar ratio of the charged amount of the compound represented by the general formula (8) and the polycarbonate diol is preferably 1.1: 1 to 6: 1, and more preferably 1.5: 1 to 3: 1.
In the case of using an alkylenediol together, the molar ratio of the charged amount of the compound represented by the general formula (8) and the alkylene diol is preferably 1.1: 1 to 6: 1, more preferably 1.5: 1 to 3: 1. preferable.

A conventionally known transesterification catalyst can be used as the transesterification reaction catalyst. Specifically, alkali metals, alkaline earth metals, oxides and weak acid salts thereof; oxides of Mn, U, Zn, Cd, Zr, Pb, Ti, Co, and Sn, hydroxides, inorganic acid salts, Examples include alcoholates and organic acid salts; organic tin compounds such as dibutyltin oxide, dioctyltin oxide, and dibutyltin dichloride. Among these, tetraisopropoxy titanium, tetrabutoxy titanium, dibutyl tin oxide, dioctyl tin oxide, acetylacetone hafnium, and acetylacetone zirconium are preferable, and dibutyltin oxide and dioctyltin oxide are more preferable.

The amount of the catalyst used varies depending on the activity of the catalyst, but an amount that can distill allyl alcohol at an appropriate rate is used. Generally, about 0.0001 to 1% by mass, preferably about 0.001 to 0.5% by mass is used with respect to the diallyl ester compound represented by the general formula (8).

The reaction temperature in this production process is preferably less than 180 ° C, more preferably 170 ° C or less, and further preferably 160 ° C or less. Increasing the reaction temperature shortens the reaction time, but there is a possibility of coloring and increasing the amount of by-products.

As an embodiment of the reaction, in order to promote the progress of the reaction, it is preferable to carry out the reaction under reduced pressure, using an appropriate solvent, and the like while removing by-product allyl alcohol from the reaction system.

(C) Polyfunctional (meth) acrylic compound:
The curable composition of the present invention contains a polyfunctional (meth) acrylic compound. In the present specification, the polyfunctional (meth) acrylic compound means an organic compound having two or more (meth) acryloyloxy groups, and is a component that contributes to the development of high surface hardness of the cured product.
The polyfunctional (meth) acrylic compound is mainly composed of a (meth) acrylate monomer or oligomer having 10 to 30 carbon atoms having 3 or more (meth) acryloyloxy groups in terms of dimensional stability. A compound having an aliphatic or alicyclic skeleton having no aromatic ring in the molecule is preferable from the viewpoint of transparency. Specifically, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris ( 2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tet (Meth) acrylate, dipentaerythritol tri (meth) acrylate. More preferred specific examples include trimethylolpropane tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Dipentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, dicyclopentanyldimethylene di (meth) acrylate and / or 5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) ) -5- (hydroxymethyl) -1,3-dioxadi (meth) acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,3-butanediol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol di (meth) acrylate Propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, zinc di (meth) acrylate, bisphenol A-diglycidyl ether di (meth) acrylate, bisphenol A-ethylene oxide modified di (meth) acrylate, hydrogenated bisphenol A- Diglycidyl ether di (meth) acrylate, hydrogenated bisphenol A-ethylene oxide modified di (meth) acrylate, bisphenol F-diglycidyl ether diacrylate, bisphenol F-ethylene oxide modified di (meth) acrylate, hydrogenated bisphenol F-diglycidyl ether Di (meth) acrylate, hydrogenated bisphenol F-ethylene oxide modified di (meth) acrylate, neopentyl glycol diglycidyl ether di ( E) esterifying epoxy (meth) acrylate such as acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, polyhydric alcohol and polyhydric carboxylic acid and / or anhydride thereof and acrylic acid Reactive diluent for bifunctional (meth) acrylic compounds such as urethane di (meth) acrylate obtained by reacting the resulting polyester di (meth) acrylate, polyhydric alcohol, polyvalent isocyanate and hydroxyl group-containing (meth) acrylate Can also be used in combination. These polyfunctional (meth) acrylic compounds may be used alone or in combination of two or more.

In the present specification, the (meth) acrylic compound means a methacrylic compound or an acrylic compound, similarly (meth) acrylate means methacrylate or acrylate, and (meth) acryloyloxy group means methacryloyloxy group or acryloyloxy. Means a group.

The amount of the polyfunctional (meth) acrylic compound used as the component (C) is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the component (A). If the amount of the (meth) acrylic compound is too small, the hardness of the film is difficult to be obtained, and the scratch resistance may be deteriorated. On the other hand, if the amount is too large, cracks may occur as the curing shrinks.

(D) Polymerization initiator:
The curable composition of the present invention contains a polymerization initiator for obtaining a cured product. As the polymerization initiator, a photopolymerization initiator (D1) or a thermal polymerization initiator (D2) can be used. The photopolymerization initiator (D1) and the thermal polymerization initiator (D2) can be used either alone or in combination.

As the photopolymerization initiator (D1), a photocleavable type and / or a hydrogen abstracting type that can be easily cleaved to form two radicals by known ultraviolet irradiation, or a mixture thereof can be used. These compounds include benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, hydroxybenzophenone, benzophenones such as 4,4'-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin isobutyl Benzoin alkyl ethers such as ether, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) -butanone-1, thioxanthene, 2-chlorothioxanthene, 2-methylthioxanthene, 2,4-di Thioxanthenes such as tilthioxanthene, alkylanthraquinones such as ethyl anthraquinone and butyl anthraquinone, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethane Benzyldimethylketals such as -1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Α-aminoketones such as morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy Α-hydroxy ketones such as -2-methyl-propan-1-one, , Mention may be made of 10-phenanthrenequinone and the like. These can be used alone or as a mixture of two or more.

The blending amount of the photopolymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount is less than 0.1 parts by mass, the photocurability is insufficient, and if it exceeds 10 parts by mass, the solvent resistance and flexibility are deteriorated.

Also, when a photopolymerization initiator is used and polymerized and cured with ultraviolet rays, a photosensitizer can be used in combination as necessary in order to improve the polymerization rate. Examples of the sensitizer used for such purpose include pyrene, perylene, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, phenothiazine and the like. The amount of the sensitizer used in combination is preferably in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the photopolymerization initiator.

As the thermal polymerization initiator (D2), a known organic peroxide or azo compound can be used. Examples of the organic peroxide include diacyl peroxides [dibenzoyl peroxide, lauroyl peroxide, etc.], dialkyl peroxides [di-tert-butyl peroxide, dicumyl peroxide, etc.]; peroxyesters [tert -Butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, etc.]; Ketone peroxides [methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.]; Peroxydicarbonates [Bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, etc.]; Peroxymonocarbonate type [tert-butylperoxyisopropylcarbonate, etc.] Peroxyketal type [1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2-bis (tert-butylperoxy) octane, etc.]; and two or more of these A mixture is mentioned. Among these, peroxyester organic peroxides are preferable.

Examples of the azo compound include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, dimethyl-2,2'-azobisisobutyrate, and the like.

These thermal polymerization initiators can be used alone or as a mixture of two or more. The blending amount of the thermal polymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount is less than 0.1 parts by mass, the thermosetting property may be insufficient. On the other hand, if it exceeds 10 parts by mass, the solvent resistance and flexibility are unfavorable.

The curable composition of the present invention is an ultraviolet absorber, an antioxidant, a mold release agent, a lubricant, for the purpose of improving hardness, strength, moldability, durability, and water resistance within a range that does not interfere with the effects of the present invention. Various known additives such as colorants, flame retardants, crosslinking aids, inorganic fillers, organic fillers, polymerization inhibitors, thickeners, antifoaming agents, leveling agents, and adhesion promoters can be used. . In particular, those that do not inhibit the light transmittance are preferred.

Specific examples of UV absorbers include triazoles such as 2- (2′-hydroxy-tert-butylphenyl) benzotriazole, benzophenones such as 2,4-dihydroxybenzophenone, 4-tert-butylphenyl salicylate, etc. Of salicylates.

The blending amount of the ultraviolet absorber varies depending on the type and amount of the other blends, but is generally 0.01 to 2 parts by weight with respect to 100 parts by weight of all radical polymerizable components in the composition for optical materials. Part is preferable, 0.03 to 1.7 parts by weight is more preferable, and 0.05 to 1.4 parts by weight is most preferable. If the ultraviolet absorber is less than 0.01 parts by mass, a sufficient effect cannot be expected, and if it exceeds 2 parts by mass, it is economically undesirable.

Antioxidants include 2,6-di-tert-butyl-4-methylphenol, tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, etc. Phenol-based, sulfur-based dilauryl-3,3′-thiodipropionate, etc., phosphorus-based antioxidants such as trisnonylphenyl phosphite, bis- (2,2,6,6-tetramethyl-4- Hindered amines such as piperidinyl) sebacate and the like.

The blending amount of the antioxidant varies depending on the type and amount of other blends, but is generally 0.01 to 5 with respect to 100 parts by weight of all radically polymerizable components in the composition for optical materials. Part by mass is preferable, 0.05 to 4 parts by mass is more preferable, and 1 to 3 parts by mass is most preferable. If the antioxidant is less than 0.01 parts by mass, a sufficient effect cannot be expected, and if it exceeds 5 parts by mass, it is economically undesirable.

Examples of the mold release agent include stearic acid, butyl stearate, zinc stearate, stearic acid amide, fluorine-based compounds, and silicone compounds. The compounding amount of the release agent varies depending on the type and amount of other compounds, but is generally 0.01 to 2 with respect to 100 parts by mass of all radical polymerizable components in the composition for optical materials. Part by mass is preferred, 0.03 to 1.7 parts by mass is more preferred, and 0.05 to 1.4 parts by mass is most preferred. If the release agent is less than 0.01 parts by mass, a sufficient effect cannot be expected, and if it exceeds 2 parts by mass, it is not economically preferable.

There is no restriction | limiting in particular as a lubricant, What is generally used can be used. Among these, metal soap lubricants, fatty acid ester lubricants, aliphatic hydrocarbon lubricants and the like are preferable, and metal soap lubricants are particularly preferable. Examples of the metal soap lubricant include barium stearate, calcium stearate, zinc stearate, magnesium stearate and aluminum stearate. These may be used as a complex.

Colorants include anthraquinone, azo, carbonium, quinoline, quinoneimine, indigoid, phthalocyanine and other organic pigments, azoic dyes, sulfur dyes and other organic dyes, titanium yellow, yellow iron oxide, zinc yellow, Examples thereof include inorganic pigments such as chromium orange, molybdenum red, cobalt purple, cobalt blue, cobalt green, chromium oxide, titanium oxide, zinc sulfide, and carbon black. The blending amount is not particularly limited.

Specific examples of the flame retardant include brominated epoxy compounds, acid-modified brominated epoxy compounds, brominated epoxy compounds having an acryloyl group, bromine-containing compounds such as acid-modified brominated epoxy compounds having an acryloyl group, red phosphorus, Inorganic flame retardants such as tin oxide, antimony compounds, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide, ammonium phosphate compounds, phosphate compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters And phosphorus compounds such as nitrogen-containing phosphorus compounds and phosphazene compounds.

The blending amount of the flame retardant varies depending on the type and amount of other blends, but generally 10 to 50 parts by weight with respect to 100 parts by weight of all radical polymerizable components in the composition for optical materials. preferable. If the flame retardant is less than 10 parts by mass, a sufficient flame retardant effect cannot be expected, and if it exceeds 50 parts by mass, the transparency is undesirably lowered.

Specific examples of the crosslinking aid are compounds that act as a crosslinking aid in the partial crosslinking treatment with a thermal polymerization initiator, and examples thereof include polyfunctional vinyl monomers such as divinylbenzene and triallyl cyanurate. The amount of the crosslinking aid varies depending on the type and amount of the other compound, but is generally 1 to 30 parts by mass with respect to 100 parts by mass of all radical polymerizable components in the composition for optical materials. Is preferred. If the crosslinking aid is less than 1 part by mass, a sufficient effect cannot be expected, and if it exceeds 30 parts by mass, the flexibility of the film is lowered, which is not preferable.

Specific examples of the inorganic filler include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, crystalline silica, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, Although well-known and usual inorganic fillers, such as a mica powder, a glass sphere, glass fiber, and carbon fiber, can be illustrated, it is not limited to these. As specific examples of the organic filler, known organic fillers such as acrylic resin, melamine resin, styrene resin, silicone resin, silicone rubber, and fluorine resin can be used, but the organic filler can be exemplified. is not. These inorganic fillers and organic fillers can be used singly or in combination of two or more, and are within the range not impairing the gist of the present invention, that is, 100 parts by mass of all radical polymerizable components in the composition for optical materials. 1 to 50 parts by mass can be added.

Further, if necessary, known and conventional polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol and phenothiazine, known and conventional thickeners such as silica, asbestos, olben, benton and montmorillonite, silicone type , Fluorine-based, acrylic-based, polymer-based and other antifoaming agents and / or known conventional additives such as leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agents and other adhesion-imparting agents Can be added as long as the gist of the present invention is not impaired.

These additives are not limited to the specific examples described above, and any additives can be added within a range that does not impair the object or effect of the present invention.

When curing the curable composition of the present invention, a solvent may be used if it is necessary to reduce the viscosity by a curing method. Examples of solvents that can be used for viscosity adjustment include aromatic hydrocarbons such as toluene and xylene, acetates such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones, ethers such as tetrahydrofuran and 1,4-dioxane, and alcohols such as ethyl alcohol, (iso) propyl alcohol, and butyl alcohol. However, since it is necessary to remove the solvent later, the viscosity is preferably adjusted with a component (C) polyfunctional (meth) acrylic compound that can also be used as a reactive viscosity modifier.

In producing an optical resin film or sheet from the curable composition of the present invention, any curing method may be selected as long as a certain surface hardness is obtained. In order to obtain a surface hardness of a certain level or more, it is preferable to apply only a photocuring and thermosetting method or a thermosetting method after coating the curable composition into a film shape.

The conditions for curing the curable composition are not particularly limited, but after being applied and cast on a transparent plastic film, metal sheet, or glass plate, photocuring and thermosetting, or thermosetting is performed. It is preferred to implement.

In the case of photocuring, an ultraviolet irradiation method is generally used. For example, ultraviolet rays can be generated and irradiated using an ultraviolet lamp. Examples of ultraviolet lamps include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, pulse-type xenon lamps, xenon / mercury mixed lamps, low-pressure sterilization lamps, electrodeless lamps, and LED lamps, all of which can be used. Among these ultraviolet lamps, a metal halide lamp or a high-pressure mercury lamp is preferable. Irradiation conditions vary depending on each lamp condition, but the irradiation exposure dose is preferably about 20 to 5000 mJ / cm ² . In addition, it is preferable to attach an elliptical, parabolic, diffusive or the like reflector to the ultraviolet lamp, and a heat cut filter or the like as a cooling measure. Further, in order to accelerate curing, it may be preheated to 30 to 80 ° C. and irradiated with ultraviolet rays.

In the case of thermosetting, the heating method is not particularly limited, but a heating method excellent in uniformity such as a hot air oven or a far infrared oven is preferable. The curing temperature is about 100 to 200 ° C, preferably 120 to 180 ° C. Although the curing time varies depending on the curing method, it is preferably 0.5 to 5 hours for a hot air oven and 0.5 to 60 minutes for a far infrared oven.

In addition, ultraviolet curing using a photopolymerization initiator and thermal curing using an organic peroxide or an azo compound are radical reactions and thus are susceptible to reaction inhibition by oxygen. In order to prevent oxygen inhibition during the curing reaction, the resin composition is curable when coated and cast on a transparent plastic film, metal sheet, or glass plate, followed by photocuring and / or thermosetting. It is preferable to apply a transparent cover film on the varnish and to reduce the oxygen concentration on the surface of the cast curable composition to 1% or less. It is necessary to use a transparent cover film that does not have pores on the surface, has a low oxygen permeability, and can withstand the heat generated during ultraviolet curing or thermal curing. For example, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), PP (polypropylene), acetate resin, acrylic resin, vinyl fluoride, polyamide, polyarylate, polyethersulfone, norbornene resin, etc. These are films, and these can be used alone or in combination of two or more. However, since it must be possible to peel from the cured product after curing, the surface of these transparent cover films may be subjected to easy peeling treatment such as silicone resin coating or fluororesin coating.

Since the curable composition of the present invention is in a liquid state, it can be applied and coated so as to have a predetermined shape and form using a known coating apparatus. Coating methods include gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, wire bar coating, curtain coating, extrusion coating, spinner coating, casting molding method, Known methods such as stereolithography can be used. The preferred viscosity range at this time is in the range of 100 to 100,000 mPa · s at room temperature.

Hereinafter, the present invention will be further described with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these descriptions.

The physical properties of the allyl ester oligomers obtained in Synthesis Examples 1 to 3 were determined by the following measuring methods.
[Hazen color number]
Based on JIS K0071, the Hazen color number of the allyl ester oligomer was measured by comparison with a standard solution using a colorimetric tube.
[viscosity]
Model used: TVE-20H manufactured by Toki Sangyo Co., Ltd.
Measuring method: cone plate viscometer, rotor No. Measurement was performed at a liquid temperature of 25 ° C. and 10 rpm using a rotor of 1 ° 34 ′ × R24.
[Number average molecular weight]
Model used: GPC system SIC-480II manufactured by Showa Denko KK
Column: Showa Denko KPC column K-801, K-802, K-802.5
Detector: Showa Denko Co., Ltd. RI-201H
Eluent: Chloroform measurement method: 100 μL of a sample dissolved in chloroform was introduced into a column controlled at 40 ° C., and the number average molecular weight in terms of polystyrene was measured.

Various physical properties of the cured films obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated by the following methods.
[Total light transmittance]
With respect to a film having a thickness of 0.1 mm, total light transmittance was determined as an index of optical characteristics using NDH-2000 manufactured by JEOL Ltd. according to JIS K7361-1. In the present specification, “highly transparent” means that the total light transmittance is 85% or more.
[Tensile modulus]
A strip-shaped film piece (length: 150 mm, width: 15 mm) was cut out from a film having a thickness of 0.1 mm, and a distance between chucks: 100 mm using a tensile tester [Universal Tester Autograph manufactured by Shimadzu Corporation]. , Crosshead speed: Tensile test was performed under the condition of 5 mm / min, and tensile modulus (GPa) was obtained as an index of flexibility.
[Machinability]
Using the curable compositions of Examples 1 and 2 and Comparative Examples 1 and 2, cured films having a thickness of 0.5 mm were prepared in the same manner, and these cured films were processed by NC router processing machine “Machino Technica Machining Center NCK1210F”. -1 ATV ", the sample was cut out under conditions of a spindle rotation speed of 50,000 rpm and a feed rate of F 1000 mm / min. Using a digital microscope “Keyence VHX900” on the processed surface, the portions lacking in a length of 30 μm or more observed in the field of view with a lens magnification of 300 times were visually counted to obtain an index of workability.
Missing number 0-9: ○
Number of chipping 10 or more: ×
[Heat-resistant]
As an index of heat resistance, an average thermal expansion coefficient was measured in a tensile mode using EXSTER TMA / SS6100 manufactured by SII Nanotechnology. The film-like test piece is 0.1 mm × 4 mm × 20 mm in thickness, 30 N in load, and in a nitrogen atmosphere, the temperature is raised to 200 ° C. at a temperature rising rate of 5 ° C./min. The difference in the average thermal expansion coefficient was determined.
Difference in average thermal expansion coefficient = average thermal expansion coefficient (150 to 200 ° C)-average thermal expansion coefficient (0 to 50 ° C)
Heat resistance ○: Difference in average thermal expansion coefficient is less than 50 ppm / K Heat resistance x: Difference in average thermal expansion coefficient is 50 ppm / K or more [surface hardness]
In accordance with JIS K5600-5-4, tilt the pencil-shaped pencil lead to a 45 degree angle, apply a load of 750 g from the top, scratch the surface of the object to be measured about 5 mm, and check for scratches. Pencil hardness was determined as an index of surface hardness.

Synthesis Example 1: Synthesis of allyl ester oligomer (AEO) [a1] 400 g of diallyl 1,4-cyclohexanedicarboxylate (manufactured by Showa Denko KK), 60 g of trimethylolpropane (TMP manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight 134) 60 g Then, 1.0 g of dioctyltin oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a three-necked flask and heated to react with an oil bath adjusted to 180 ° C. Allyl alcohol produced with the progress of the reaction was distilled off. The reaction was gradually reduced from normal pressure to 1.4 kPa, and the reaction was terminated when the theoretical amount of allyl alcohol was distilled off. The reaction time was about 12 hours. After cooling, the reaction solution was taken out to obtain 353 g of allyl ester oligomer (AEO). The obtained AEO was liquid at room temperature, had a Hazen color number of 15, a viscosity at 25 ° C. of 1800 mPa · s, and a polystyrene-equivalent number average molecular weight of 820.

Synthesis Example 2: Synthesis of allyl ester oligomer (PCD-1) [b1] 400 g diallyl 1,4-cyclohexanedicarboxylate (Showa Denko), polycarbonate diol (C590, Kuraray Co., Ltd., number average molecular weight 500) 400 g and dioctyltin oxide (Tokyo Chemical Industry Co., Ltd.) 0.4 g were charged into a three-necked flask and heated in an oil bath adjusted to 160 ° C. for reaction. Allyl alcohol produced with the progress of the reaction was distilled off. The reaction was gradually reduced from normal pressure to 1.4 kPa, and the reaction was terminated when the theoretical amount of allyl alcohol was distilled off. The reaction time was about 8 hours. After cooling, the reaction solution was taken out to obtain 692 g of flexible allyl ester oligomer (PCD-1). The obtained PCD-1 was liquid at room temperature, had a Hazen color number of 15, a viscosity at 25 ° C. of 3200 mPa · s, and a polystyrene-equivalent number average molecular weight of 1300.

Synthesis Example 3: Synthesis of allyl ester oligomer (PCD-2) [b2] 400 g diallyl 1,4-cyclohexanedicarboxylate (produced by Showa Denko KK), polycarbonate diol (UHC 50-100 produced by Ube Industries), number average 800 g of molecular weight 1000) and 0.8 g of dioctyltin oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a three-necked flask and heated in an oil bath adjusted to 160 ° C. for reaction. Allyl alcohol produced with the progress of the reaction was distilled off. The reaction was gradually reduced from normal pressure to 1.4 kPa, and the reaction was terminated when the theoretical amount of allyl alcohol was distilled off. The reaction time was about 10 hours. After cooling, the reaction solution was taken out to obtain 1025 g of flexible allyl ester oligomer (PCD-2). The resulting PCD-2 was liquid at room temperature, had a Hazen color number of 50, a viscosity at 25 ° C. of 5500 mPa · s, and a polystyrene-equivalent number average molecular weight of 2000.

Example 1:
15 parts by mass of the allyl ester oligomer (PCD-1) obtained in Synthesis Example 2 and trimethylolpropane triacrylate (trade name; A-TMPT, new) with respect to 100 parts by mass of the allyl ester oligomer AEO obtained in Synthesis Example 1 30 parts by mass of Nakamura Chemical Co., Ltd., 1,4 parts of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name; LUCIRIN TPO, manufactured by BASF Japan Ltd.), and tert-hexyl par 1 part by mass of oxyisopropyl monocarbonate (trade name; Perhexyl I, manufactured by Nippon Oil & Fats Co., Ltd.) was added and sufficiently stirred to obtain a curable composition.
This curable composition was applied onto a PET film having a thickness of 0.1 mm, and further laminated with a PET film having a thickness of 0.1 mm. This laminated film was irradiated with UV under the conditions of a peak illuminance of 300 mW / cm ² and an irradiation amount of 800 mJ / cm ² with a UV irradiator having a metal halide lamp to produce a UV cured laminated film. Furthermore, after thermosetting at 160 ° C. for 1 hour in an oven under an air atmosphere, it was cooled to room temperature. By peeling the PET film from both sides of the laminated film, a cured film having a thickness of about 0.1 mm obtained by curing the curable composition was produced.
Table 1 summarizes the composition of the curable composition and the evaluation results of the cured film.

Example 2:
A curable composition was prepared and a cured film was prepared in the same manner as in Example 1 except that the allyl ester oligomer (PCD-2) obtained in Synthesis Example 3 was used instead of the allyl ester oligomer (PCD-1). The characteristics of the cured film were evaluated.
Table 1 summarizes the composition of the curable composition and the evaluation results of the cured film.

Comparative Example 1:
A curable composition was prepared in the same manner as in Example 1 except that no allyl ester oligomer (PCD-1) was added, a cured film was prepared, and the characteristics of the cured film were evaluated.
Table 1 summarizes the composition of the curable composition and the evaluation results of the cured film.

Comparative Example 2:
30 parts by mass of A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 600 diacrylate (having 14 ethylene oxide units)) and 2,4 parts per 100 parts by mass of the allyl ester oligomer AEO obtained in Synthesis Example 1 , 6-Trimethylbenzoyl-diphenyl-phosphine oxide (trade name; LUCIRIN TPO, manufactured by BASF Japan Ltd.) and 1 part by weight of tert-hexyl peroxyisopropyl monocarbonate (trade name; Perhexyl I, Nippon Oil & Fats Co., Ltd.) 1) 1 part by mass was added and stirred sufficiently to obtain a curable composition. Using the obtained curable composition, the cured film was produced like Example 1, and the characteristic of the cured film was evaluated.
Table 1 summarizes the composition of the curable composition and the evaluation results of the cured film.

From the comparison of the results of Examples 1 and 2 and Comparative Example 1, the total light transmittance, heat resistance, and surface hardness are maintained by using a curable composition containing an allyl group-terminated allyl ester oligomer containing a carbonate structure. However, it can be seen that the tensile modulus was reduced, the processability was improved, and the cured product was given flexibility. On the other hand, in the comparative example 2 which mix | blended the acrylic compound generally used for a softness | flexibility provision, the heat resistance and surface hardness fell significantly with the fall of the tensile elasticity modulus of hardened | cured material.

Since the curable composition of the present invention can be polymerized and cured, a transparent molded article suitable for optical applications having high flexibility and excellent heat resistance, handling properties, and high surface hardness can be obtained. It is useful for optical applications such as optical sheets, optical waveguides, optical lenses, optical sealants, optical adhesives, and light guide plates.

Claims (14)

1. (A) General formula (1)
   

   

   (Wherein X ¹ represents an organic residue derived from a divalent carboxylic acid or carboxylic acid anhydride having an alicyclic structure) and has at least three end groups represented by the general formula ( 2)
   

   

   (In the formula, X ² represents an organic residue derived from a divalent carboxylic acid or carboxylic anhydride having an alicyclic structure, and Y ¹ has 2 to 20 carbon atoms having 3 to 6 hydroxyl groups. Represents an organic residue derived from a polyhydric alcohol, wherein Y ¹ represents an ester bond, a group represented by the above general formula (1) as a terminal group, and a structural unit represented by the above general formula (2). An allyl group-terminated allyl ester oligomer having a structure represented by:
   (B) General formula (3)
   

   

   (Wherein X ³ represents an optionally substituted cycloalkylene group having 5 to 10 carbon atoms or an optionally substituted alkylene group having 2 to 10 carbon atoms) and formula (4)
   

   

   As well as the end group represented by formula (5)
   

   

   (Wherein R ¹ and R ² each independently represents an alkylene group having 2 to 20 carbon atoms which may have an alkyl branch, and X ⁴ may have a substituent having 5 to 10 carbon atoms) A cycloalkylene group or an alkylene group having 2 to 10 carbon atoms which may have a substituent, and n and m represent any natural number.)
   An allyl group-terminated allyl ester oligomer having a structure represented by the formula:
   A curable composition comprising (C) a polyfunctional (meth) acrylic compound; and (D) a polymerization initiator.
2. The allyl group-terminated allyl ester oligomer (B) is further represented by the general formula (6)
   

   

   (Wherein R ³ represents an alkylene group having 2 to 20 carbon atoms which may have an alkyl branch, and X ⁵ represents a cycloalkylene group or substituent having 5 to 10 carbon atoms which may have a substituent. Represents an optionally substituted alkylene group having 2 to 10 carbon atoms, and q represents an arbitrary natural number.)
   The curable composition of Claim 1 which has a structure shown by these.
3. 1 to 40 parts by mass of the allyl group-terminated allyl ester oligomer (B) and 5 to 60 parts by mass of the polyfunctional (meth) acrylic compound (C) are polymerized per 100 parts by mass of the allyl group-terminated allyl ester oligomer (A). 3. The photopolymerization initiator (D1) is contained in an amount of 0.1 to 10 parts by mass and the thermal polymerization initiator (D2) is contained in an amount of 0.1 to 10 parts by mass as the initiator (D). Curable composition.
4. In the general formulas (1) and (2), X ¹ and X ² may each independently have a substituent, 1,2-cyclohexylene group, 1,3-cyclohexylene group, The curable composition according to any one of claims 1 to 3, which is a 1,4-cyclohexylene group or a norbornylene group.
5. The Y ¹ in the general formula (2) is an organic residue derived from a polyhydric alcohol having 3 or 4 hydroxyl groups and having 5 to 10 carbon atoms. Curable composition.
6. The allyl group terminal allyl ester oligomer (A) is represented by the following formula:
   

   

   (Wherein r represents an arbitrary natural number), or
   

   

   (In the formula, s represents an arbitrary natural number.)
   The curable composition according to any one of claims 1 to 5, which is represented by:
7. X ³ , X ⁴ and X ^{5 in the} general formulas (3), (5) and (6) are each independently 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1, The curable composition according to any one of claims 1 to 6, which is a 4-cyclohexylene group or a norbornylene group.
8. The curing according to any one of claims 1 to 7, wherein at least one of R ¹ , R ² and R ^{3 in} the general formulas (5) and (6) is an alkylene group having an alkyl branch having 1 to 4 carbon atoms. Sex composition.
9. The curable composition according to any one of claims 1 to 8, wherein R ¹ and R ² in the general formula (5) are a 1,6-hexylene group or a 2-methyl-1,5-pentylene group.
10. The curable composition according to any one of claims 1 to 8, wherein R ¹ and R ² in the general formula (5) are nonylene groups.
11. In the allyl group-terminated allyl ester oligomer (B), R ¹ represents R ⁴ , R ² represents R ⁵ , and X ³ and X ⁴ are 1,4-cyclohexylene groups (7)
    

    

    (In the formula, R ⁴ and R ⁵ each independently represents a 1,6-hexylene group or a 2-methyl-1,5-pentylene group, and n and m represent an arbitrary natural number.)
    The curable composition according to any one of claims 1 to 10, which is an oligomer compound represented by the formula:
12. The polyfunctional (meth) acrylic compound (C) is mainly composed of a (meth) acrylate monomer or oligomer having three or more (meth) acryloyloxy groups. Curable composition.
13. An optical material obtained by curing the curable composition according to any one of claims 1 to 12 by applying light and / or heat.
14. An optical film, an optical sheet, an optical waveguide, an optical lens, an optical sealant, an optical adhesive, or a light guide plate using the optical material according to claim 13.