The present invention relates to cyclic olefin resin compositions, molded articles and optical components.
Background technology
[0002]
Cyclic olefin copolymers are used as optical components such as optical lenses because they have excellent optical performance.
Examples of techniques related to cyclic olefin copolymers used in optical components include those described in Patent Document 1 (Japanese Patent Laid-Open No. 2013-209501) and Patent Document 2 (Japanese Patent Laid-Open No. 2009-108282). ..
[0003]
In Patent Document 1, nano-dispersion in which particles of an inorganic compound having an average particle size of 100 nm or less are dispersed in a matrix of a terminal-modified vinyl alicyclic hydrocarbon polymer hydride containing a functional group at the end of a molecular chain. The body is disclosed. Patent Document 1 describes that an optical lens having a high refractive index can be obtained by using such a nanodisperse.
[0004]
Patent Document 2 describes an alicyclic structure-containing polymerizable monomer having a silicon-containing group having a specific structure and an alicyclic structure having a carbon-carbon double bond in the ring and not having an aromatic ring structure. (A) An alicyclic structure-containing polymerizable monomer (B) having an aromatic ring structure and an alicyclic structure having a carbon-carbon double bond in the ring, and having 5 to 30% by weight and no silicon atom. ) 50 to 90% by weight and 0 to 45% by weight of the polymerizable monomer (C) copolymerizable with these, at least the alicyclic structure-containing weight obtained by polymerizing the polymerizable monomer composition. The coalescence is disclosed. Patent Document 2 describes that an optical lens having a high refractive index, a high Abbe number, and a high light transmittance can be obtained by using such an alicyclic structure-containing polymer.
Advanced technical literature
Patent documents
[0005]
Patent Document 1: Japanese Patent Application Laid-Open No. 2013-209501
Patent Document 2: Japanese Patent Application Laid-Open No. 2009-108282
Outline of the invention
Problems to be solved by the invention
[0006]
Further improvement of the refractive index is required in optical component applications such as optical lenses that are required to be smaller and thinner.
The present invention has been made in view of the above circumstances, and provides a cyclic olefin resin composition capable of realizing an optical component having transparency and a high refractive index.
Means to solve problems
[0007]
The present inventors have diligently studied to solve the above problems. As a result, the cyclic olefin resin can realize an optical component having an excellent balance of transparency and high refractive index performance by finely dispersing inorganic fine particles whose surface is modified by a modifier with respect to the cyclic olefin copolymer. They have found that a composition can be obtained and have completed the present invention.
[0008]
The present invention is as shown below.
[0009]
[1]
A cyclic olefin resin composition containing a cyclic olefin copolymer (A) and
inorganic fine particles (B) whose surface is modified with a modifier
, wherein the
modifier is a phosphoric acid ester or an organic substance. One or more selected from the group consisting of phosphonic acid, phosphonic acid ester, carboxylic acid, sulfonic acid, hydrocarbon compound having an amino group, and silane coupling agent, and the
cyclic olefin-based copolymer (A). A cyclic olefin-based resin composition in which the inorganic fine particles (B) are dispersed.
[2] In
the cyclic olefin resin composition according to the above [1], the modifier is a cyclic olefin resin composition which is a compound represented by the following formula (1).
R 1- X (1)
(In the formula, R 1 represents a hydrocarbon group having 3 to 18 carbon atoms, and X is a functional group or the functional group that forms a bond with the surface of the inorganic fine particles (B). represents an atomic group having
a.) [3]
above [1] or in the cycloolefin resin composition according to [2],
the cyclic olefin-based resin (a) is
the following [a-1], [a A cyclic olefin resin composition containing one or more selected from -2], [A-3] and [A-4].
[A-1] A random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formulas [I], [II], [III], [IV] or [V].
[0010]
[Chemical
formula 1] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R b are. , Independently, hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride. It is a hydrocarbon group which may be substituted with a group, an epoxy group or an amino group, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic group may be formed. The ring may have a double bond and may form an alkylidene group with R 15 and R 16 or with R 17 and R 18 ),.
[0011]
[Chemical
formula 2] (In the above formula [II], p and q are 0 or positive integers, m and n are 0, 1 or 2, and R 1 to R 19 are independently hydrogen atoms and halogen atoms, respectively. , Carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or substituted with halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group or amino group It is a hydrocarbon group or an alkoxy group that may be present, and the carbon atom to which R 9 and R 10 are bonded and the carbon atom to which R 13 is bonded or the carbon atom to which R 11 is bonded are directly or directly. It may be bonded via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R 15 and R 12 or R 15 and R 19 are bonded to each other to form a monocyclic or polycyclic fragrance. It may form a family ring.),
[0012]
[Chemical
formula 3] (In the above formula [III], n and m are independently 0, 1 or 2, q is 1, 2 or 3, and R 18 to R 31 are independently hydrogen atoms, respectively. Halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group or amino group It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and when q = 1, R 28 and R 29 , R 29 and R 30 , and R 30 and R 31 are bonded to each other and are monocyclic or It may form a polycycle, and when q = 2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31., R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may have a double bond. The ring may be an aromatic ring. ),
[0013]
[Chemical
formula 4] (In the above formula [IV], q is 1, 2 or 3, and R 32 to R 39 are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group and acid anhydride. A hydrocarbon having 1 to 20 carbon atoms which may be substituted with a physical group, an epoxy group, an amino group, or a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group. It is a group, and when q = 1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and q = 2 or When 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39And R 39 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring is aromatic. It may be a tricyclic ring. ),
[0014]
[Chemical
formula 5] (In the above formula [V], n and q are 0, 1 or 2, respectively, and R 1 to R 17 are independently hydrogen atoms, halogen atoms, carboxyl groups, hydroxyl groups, and sulfones. 1 carbon atom which may be substituted with an acid group, an acid anhydride group, an epoxy group, an amino group, or a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group. ~ 20 hydrocarbon groups, one of R 10 ~ R 17 is a bond, and when q = 0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 And R 14 , R 14 and R 15 , R 15 and R 10 may be combined with each other to form a monocyclic or polycyclic ring, and when q = 1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, or the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be formed. The polycycle may be an aromatic ring. ),
[A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the above formulas [I], [II], [III], [IV] or [V],
[A-3] the above ring-opening weight. A hydride of the coalesced or copolymer [A-2],
[A-4] a graft modified product of the above [A-1], [A-2] or [A-3].
[4] In
the cyclic olefin resin composition according to any one of the above [1] to [3], the
modifier is a phosphoric acid ester containing a hydrocarbon group having 12 to 18 carbon atoms and 12 carbon atoms. A cyclic olefin resin composition containing one or more selected from carboxylic acids containing 18 hydrocarbon groups.
[5] In
the cyclic olefin resin composition according to any one of the above [1] to [4], the cyclic olefin
copolymer (A) is a structural unit (a3) derived from a monomer having a polar group. )
Is included, and the polar group is selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group and an amino group. Alternatively, a cyclic olefin resin composition of two or more kinds.
[6] In
the cyclic olefin resin composition according to the above [5],
The content of the structural unit (a3) derived from the monomer having the polar group in the polar group-containing cyclic olefin copolymer (Aa) is the polar group-containing cyclic olefin copolymer (Aa). A cyclic olefin resin composition containing 0.1 mol% or more and 20 mol% or less when the total of all the constituent units constituting the above is 100 mol%.
[7] In
the cyclic olefin resin composition according to the above [5] or [6], the
polar group-containing cyclic olefin copolymer (Aa) is a monomer having the polar group and the cyclic olefin. Cyclic olefin resin composition containing one or more selected from a random copolymer (A1) and a graft copolymer (A2) obtained by grafting or graft-polymerizing a monomer having a polar group on a cyclic olefin polymer. thing.
[8] In
the cyclic olefin resin composition according to the above [7], the
polar group-containing cyclic olefin copolymer (Aa) is a structural unit derived from α-olefin having 2 to 20 carbon atoms. (A1), a structural unit (a2) derived from a cyclic olefin represented by the following formulas [I], [II], [III], [IV] or [V], and a structural unit derived from a monomer having the above polar group (a3). ), A cyclic olefin resin composition containing the random copolymer (A1).
[0015]
[Chemical
formula 6] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R b are. , Independently, hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride. It is a hydrocarbon group or an alkoxy group that may be substituted with a group, an epoxy group or an amino group, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic group, and the single ring or polycycle is formed. The ring or polycycle may have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group.)
[0016]
[Chemical
formula 7] (In the above formula [II], p and q are 0 or positive integers, m and n are 0, 1 or 2, and R 1 to R 19 are independently hydrogen atoms and halogen atoms, respectively. , Carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or substituted with halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group or amino group It is a hydrocarbon group or an alkoxy group that may be present, and the carbon atom to which R 9 and R 10 are bonded and the carbon atom to which R 13 is bonded or the carbon atom to which R 11 is bonded are directly or directly. It may be bonded via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R 15 and R 12 or R 15 and R 19 are bonded to each other to form a monocyclic or polycyclic fragrance. It may form a family ring.)
[0017]
[Chemical
formula 8] (In the above formula [III], n and m are independently 0, 1 or 2, q is 1, 2 or 3, and R 18 to R 31 are independently hydrogen atoms, respectively. Halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group or amino group It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and when q = 1, R 28 and R 29 , R 29 and R 30 , and R 30 and R 31 are bonded to each other and are monocyclic or It may form a polycycle, and when q = 2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31., R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may have a double bond. The ring may be an aromatic ring. )
[0018]
[Chemical
formula 9] (In the above formula [IV], q is 1, 2 or 3, and R 32 to R 39 are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group and acid anhydride. A hydrocarbon having 1 to 20 carbon atoms which may be substituted with a physical group, an epoxy group, an amino group, or a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group. It is a group, and when q = 1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and q = 2 or When 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39And R 39 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring is aromatic. It may be a tricyclic ring. )
[0019]
[Chemical
formula 10] (In the above formula [V], n and q are 0, 1 or 2, respectively, and R 1 to R 17 are independently hydrogen atoms, halogen atoms, carboxyl groups, hydroxyl groups, and sulfones. 1 carbon atom which may be substituted with an acid group, an acid anhydride group, an epoxy group, an amino group, or a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group. ~ 20 hydrocarbon groups, one of R 10 ~ R 17 is a bond, and when q = 0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 And R 14 , R 14 and R 15 , R 15 and R 10May combine with each other to form monocyclic or polycyclic, and when q = 1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , and R 16 and R 10 combine with each other to form a monocyclic or polycyclic. Also, the monocyclic or polycyclic may have a double bond, and the monocyclic or polycyclic may be an aromatic ring. )
[9] In
the cyclic olefin resin composition according to the above [8],
the structural unit (a2) derived from the cyclic olefin in the random copolymer (A1) is bicyclo [2.2.1] -2. -Heptene and tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-one selected from dodecene or cyclic olefin resin composition comprising repeat units derived from two or more compounds.
[10] In
the cyclic olefin resin composition according to the above [8] or [9],
the repeating unit (a1) derived from the α-olefin in the random copolymer (A1) is derived from ethylene. Cyclic olefin resin composition containing.
[11] In
the cyclic olefin resin composition according to any one of the above [8] to [10], the cyclic olefin resin composition in which the
monomer having the polar group contains the monomer represented by the following formula (10). thing.
CH 2 = CH-R 1- Xp (10)
(In the above equation (10), p is a positive integer of 1 or more and 3 or less, and R 1Is a hydrocarbon group having 0 or more carbon atoms, and X is one or more polar groups selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group and an amino group)
[ 12] In
the cyclic olefin resin composition according to the above [11], the cyclic olefin resin composition containing
one or more selected monomers having a polar group from undecenol and undecyleneic acid.
[13] In
the cyclic olefin resin composition according to the above [7], the
polar group-containing cyclic olefin copolymer (Aa) has the following formulas [I], [II], [III], [ A cyclic olefin containing a graft copolymer (A2) obtained by grafting or graft-polymerizing a monomer having the above polar group to a cyclic olefin-based polymer having a cyclic olefin-derived structural unit (a2) represented by IV] or [V]. System resin composition.
[0020]
[Chemical
formula 11] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R b are. , Independently, hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride. It is a hydrocarbon group which may be substituted with a group, an epoxy group or an amino group, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic group may be formed. The ring may have a double bond and may form an alkylidene group with R 15 and R 16 or with R 17 and R 18 ).
[0021]
[Chemical
formula 12] (In the above formula [II], p and q are 0 or positive integers, m and n are 0, 1 or 2, and R 1 to R 19 are independently hydrogen atoms and halogen atoms, respectively. , Carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or substituted with halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group or amino group It is a hydrocarbon group or an alkoxy group that may be present, and the carbon atom to which R 9 and R 10 are bonded and the carbon atom to which R 13 is bonded or the carbon atom to which R 11 is bonded are directly or directly. It may be bonded via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R 15 and R 12 or R 15 and R 19 are bonded to each other to form a monocyclic or polycyclic fragrance. It may form a family ring.)
[0022]
[Chemical
formula 13] (In the above formula [III], n and m are independently 0, 1 or 2, q is 1, 2 or 3, and R 18 to R 31 are independently hydrogen atoms, respectively. Halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group or amino group It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and when q = 1, R 28 and R 29 , R 29 and R 30 , and R 30 and R 31 are bonded to each other and are monocyclic or It may form a polycycle, and when q = 2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31., R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may have a double bond. The ring may be an aromatic ring. )
[0023]
[Chemical
formula 14] (In the above formula [IV], q is 1, 2 or 3, and R 32 to R 39 are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group and acid anhydride. A hydrocarbon having 1 to 20 carbon atoms which may be substituted with a physical group, an epoxy group, an amino group, or a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group. It is a group, and when q = 1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and q = 2 or When 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39And R 39 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring is aromatic. It may be a tricyclic ring. )
[0024]
[Chemical
formula 15] (In the above formula [V], n and q are 0, 1 or 2, respectively, and R 1 to R 17 are independently hydrogen atoms, halogen atoms, carboxyl groups, hydroxyl groups, and sulfones. 1 carbon atom which may be substituted with an acid group, an acid anhydride group, an epoxy group, an amino group, or a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group. ~ 20 hydrocarbon groups, one of R 10 ~ R 17 is a bond, and when q = 0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 And R 14 , R 14 and R 15 , R 15 and R 10May combine with each other to form monocyclic or polycyclic, and when q = 1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , and R 16 and R 10 combine with each other to form a monocyclic or polycyclic. Also, the monocycle or the polycycle may have a double bond, and the monocycle or the polycycle may be an aromatic ring. )
[14] In
the cyclic olefin resin composition according to the above [13],
the structural unit (a2) derived from the cyclic olefin in the graft copolymer (A2) is bicyclo [2.2.1] -2. -Heptene and tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-one or a cyclic olefin resin composition comprising repeat units derived from two or more compounds selected from dodecene.
[15] In
the cyclic olefin resin composition according to the above [13] or [14], the
graft copolymer (A2) is a structural unit (a1) derived from an α-olefin having 2 to 20 carbon atoms. A cyclic olefin resin composition further comprising.
[16] In
the cyclic olefin resin composition according to any one of the above [13] to [15], the
monomer having the polar group is selected from acrylic acid, methacrylic acid, maleic acid and maleic anhydride 1 A cyclic olefin resin composition containing a seed or two or more kinds.
[17] In
the cyclic olefin resin composition according to any one of the above [1] to [16], the
inorganic fine particles (B) contain one or more selected from zirconia, titania and alumina. Cyclic olefin resin composition.
[18]
The cyclic olefin resin composition according to any one of [1] to [17], wherein
the average particle diameter D 50 of the inorganic fine particles (B) is 1 nm or more and 100 nm or less.
[19] In
the cyclic olefin resin composition according to any one of the above [1] to [18],
when the total amount of the cyclic olefin resin composition is 100% by mass, the inorganic fine particles (B) A cyclic olefin resin composition having a content of 5% by mass or more and 60% by mass or less.
[20] In
the cyclic olefin resin composition according to any one of the above [1] to [19],
when a film having a film thickness of 100 μm or more and 300 μm or less is produced using the cyclic olefin resin composition. ,
A cyclic olefin resin composition having a refractive index (nD) of 1.545 or more at a wavelength of 589 nm of the film.
[21]
A molded product using the cyclic olefin resin composition according to any one of the above [1] to [20].
[22] An
optical component including the molded product according to the above [21].
The invention's effect
[0025]
According to the present invention, it is possible to provide a cyclic olefin resin composition capable of realizing an optical component having transparency and a high refractive index.
Mode for carrying out the invention
[0026]
Hereinafter, the present invention will be described based on the embodiments. In the present embodiment, "A to B" indicating a numerical range represent A or more and B or less unless otherwise specified.
[0027]
[Cyclic olefin resin composition]
First, the cyclic olefin resin composition of the embodiment according to the present invention will be described.
The cyclic olefin resin composition according to the present embodiment contains a cyclic olefin copolymer (A) and inorganic fine particles (B) whose surface is modified with a modifier. The modifier is one or more selected from the group consisting of phosphoric acid ester, organic phosphonic acid, phosphonic acid ester, carboxylic acid, sulfonic acid, hydrocarbon compound having an amino group, and silane coupling agent. Yes, the inorganic fine particles (B) are dispersed in the cyclic olefin copolymer (A).
[0028]
Here, the fact that the inorganic fine particles (B) are dispersed in the cyclic olefin copolymer (A) means that, for example, the cyclic olefin copolymer (A) is inorganic in the sea (matrix). It refers to a state in which fine particles (B) are scattered. More specifically, for example, it means a state in which the average aggregated particle size (secondary particle size) of the scattered inorganic fine particles (B) is 500 nm or less, preferably 200 nm or less, and more preferably 100 nm or less. The average agglomerated particle size (secondary particle size) of the inorganic fine particles (B) can be measured by, for example, an electron microscope.
[0029]
The cyclic olefin-based resin composition of the embodiment according to the present invention contains the cyclic olefin-based copolymer (A) and the inorganic fine particles (B) modified with the above-mentioned modifier, and by the interaction between the two. The dispersibility of the inorganic fine particles (B) in the matrix can be improved. This makes it possible to realize excellent transparency and a high refractive index in the obtained molded product and optical component.
[0030]
The content of the inorganic fine particles (B) in the cyclic olefin resin composition according to the present embodiment further increases the refractive index of the obtained optical component when the total content of the cyclic olefin resin composition is 100% by mass. From the viewpoint of improvement, 5% by mass or more is preferable, 10% by mass or more is more preferable, and from the viewpoint of further improving the transparency, refractive index, mechanical properties, and dispersibility of the inorganic fine particles (B) of the obtained optical component. , 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.
[0031]
Further, the total content of the polar group-containing cyclic olefin copolymer (A) and the inorganic fine particles (B) in the cyclic olefin resin composition according to the present embodiment is 100 for the entire cyclic olefin resin composition. When it is set to mass%, it is preferably 50% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less from the viewpoint of further improving the performance balance between the transparency and the refractive index of the obtained molded product. It is more preferably 80% by mass or more and 100% by mass or less, and particularly preferably 90% by mass or more and 100% by mass or less.
[0032]
In the cyclic olefin resin composition according to the present embodiment, when a film having a film thickness of 100 μm or more and 300 μm or less is produced using the cyclic olefin resin composition, the refractive index (nD) of the film at a wavelength of 589 nm is preferable. Is 1.545 or more, more preferably 1.550 or more, further preferably 1.554 or more, and particularly preferably 1.560 or more. When the refractive index (nD) is within the above range, the thickness can be made thinner while maintaining good optical characteristics of the obtained optical component.
[0033]
In the cyclic olefin resin composition according to the present embodiment, when a molded product is produced using the cyclic olefin resin composition, the molded product preferably has solvent resistance. The solvent resistance can be evaluated by, for example, the insoluble fraction (mass%), and the insoluble fraction (mass%) may be equal to or higher than the content of the inorganic fine particles (B) in the cyclic olefin resin composition. can.
The insoluble fraction (mass%) can be obtained, for example, as follows. A film having a film thickness of 100 μm was prepared using the cyclic olefin resin composition according to the present embodiment, and 0.3 g of the film was placed in a flask and weighed (Y (g)) to obtain a 1% by mass solution. Toluene is added so as to be, and the film is immersed at 25 ° C. for 24 hours. After 24 hours, the solvent containing the film was filtered through a membrane filter (pore diameter 10 μm) to capture the insoluble matter, dried at 25 ° C. for 48 hours, and then the mass of the insoluble matter (Z (g)) was measured. , The insoluble fraction can be calculated according to the following formula.
Insoluble fraction (mass%) = (Z / Y) x 100
[0034]
In the cyclic olefin resin composition according to the present embodiment, when a molded product is produced using the cyclic olefin resin composition, the molded product preferably has abrasion resistance. Specifically, the wear resistance can be evaluated as follows. First, a film having a film thickness of 100 μm is prepared using the cyclic olefin resin composition according to the present embodiment. Subsequently, the film is scratched with a load of 200 g using a sapphire needle having a diameter of 0.3 mm, and evaluation is performed based on the depth of the worn portion. At this time, the depth of the worn portion (scratch) is preferably less than 10 μm, and more preferably less than 5 μm.
The depth of the worn portion can be measured with, for example, a surface roughness meter.
[0035]
Hereinafter, each component will be specifically described.
[0036]
(Cyclic olefin copolymer (A))
The cyclic olefin copolymer (A) according to the present embodiment includes the following [A-1], [A-2], [A-3] and [A-]. 4] It is preferable to include one kind or two or more kinds selected from.
[A-1] number of carbon atoms is 2 ~ 20 alpha-olefin and the following formula [I], [II], [III], a random copolymer of the cyclic olefin represented by the [IV] or [V]
[ A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the formulas [I], [II], [III], [IV] or [V]
[A-3] The ring-opening polymer or Copolymer [A-2] hydride
[A-4] Graft-modified product of the above [A-1], [A-2] or [A-3]
[0037]
In [A-1], a random copolymer weight of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formulas [I], [II], [III], [IV] or [V] The α-olefin having 2 to 20 carbon atoms in the coalescence may be linear or branched. Examples of such α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. , 1-Eikosen and other linear α-olefins having 2 to 20 carbon atoms; 4-methyl-1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene and the like having carbon atoms Examples thereof include 4 to 20 branched α-olefins. Among these, a linear α-olefin having 2 to 4 carbon atoms is preferable, and ethylene is particularly preferable. Such α-olefins may be used alone or in combination of two or more.
[0038]
In [A-1], the random common weight of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formulas [I], [II], [III], [IV] or [V]. When the total of all the constituent units constituting the coalescence is 100 mol%, the content of the constituent units of the α-olefin yu ratio having 2 to 20 carbon atoms is preferably 30 mol% or more and 88 mol% or less. It is preferably 40 mol% or more and 78 mol% or less.
When the content of the structural unit derived from the α-olefin is at least the above lower limit value, the heat resistance and dimensional stability of the obtained optical component can be improved. Further, when the content of the constituent unit derived from the α-olefin is not more than the above upper limit value, the transparency of the obtained optical component can be improved.
[0039]
The cyclic olefins represented by the formulas [I], [II], [III], [IV] or [V] are shown below.
[0040]
[化16]
[0041]
In the above equation [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, Ra and R b are independently the following atoms or hydrocarbon groups, and when q is 0, the respective bonds are bonded to form a 5-membered ring. To form.
[0042]
R 1 to R 18 and Ra and R b are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl. A hydrocarbon group that may be substituted with a group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
[0043]
In addition, examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group, respectively. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and examples of the cycloalkyl group include cyclohexyl. Examples include groups, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. These hydrocarbon groups may be substituted with a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group.
[0044]
Further, in the above formula [I], R 15 to R 18 may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed. May have a double bond. Specific examples of the monocyclic or polycyclic formed here are shown below.
[0045]
[化17]
[0046]
In the above example, the carbon atoms numbered 1 or 2 indicate the carbon atoms to which R 15 (R 16 ) or R 17 (R 18 ) are bonded in the above formula [I], respectively . .. Further , an alkylidene group may be formed by R 15 and R 16 or by R 17 and R 18 . Such an alkylidene group is, for example, an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group, and an isopropylidene group.
[0047]
[化18]
[0048]
In the above formula [II], p and q are 0 or positive integers, and m and n are 0, 1 or 2. Further, R 1 to R 19 are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group and sulfonic acid. A hydrocarbon or alkoxy group that may be substituted with a group, an acid anhydride group, an epoxy group or an amino group.
[0049]
The halogen atom has the same meaning as the halogen atom in the above formula [I]. The hydrocarbon groups are, for example, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon. The group etc. can be mentioned. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and examples of the cycloalkyl group include cyclohexyl. Examples of the group include an aryl group and an aralkyl group, and specific examples thereof include a phenyl group, a trill group, a naphthyl group, a benzyl group and a phenylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and the like. These hydrocarbon groups and alkoxy groups may be substituted with halogen atoms, carboxyl groups, hydroxyl groups, sulfonic acid groups, acid anhydride groups, epoxy groups or amino groups.
[0050]
Here, the carbon atom to which R 9 and R 10 are bonded and the carbon atom to which R 13 is bonded or the carbon atom to which R 11 is bonded are directly or alkylene groups having 1 to 3 carbon atoms. It may be connected via. That is, when the above two carbon atoms are bonded via an alkylene group, the groups represented by R 9 and R 13 or the groups represented by R 10 and R 11 cooperate with each other to form a methylene group (-). It forms an alkylene group of either CH 2- ), an ethylene group (-CH 2 CH 2- ) or a propylene group (-CH 2 CH 2 CH 2- ). Further, when n = m = 0, R 15 and R 12 or R 15 and R 19May be combined with each other to form monocyclic or polycyclic aromatic rings. Examples of the monocyclic or polycyclic aromatic ring in this case include groups in which R 15 and R 12 further form an aromatic ring when n = m = 0 as described below .
[0051]
[化19]
[0052]
Here, q has the same meaning as q in the above formula [II].
[0053]
Examples of the cyclic olefin represented by the above formula [I] or [II] include, for example.
[0054]
[Chemical
formula 20] (Numbers 1 to 7 in the above formula indicate carbon position numbers) and derivatives in which a hydrocarbon group is substituted for this bicyclo [2.2.1] -2-heptene can be mentioned. Examples of the hydrocarbon group include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl and 5-methyl-5. -Phenyl, 5-benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5-( Anthracenyl), 5,6-diphenyl and the like.
[0055]
Further, examples of the cyclic olefin represented by the above formula [I] or [II] include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene and 1,4-methano. Examples thereof include bicyclo [2.2.1] -2-heptene derivatives such as -1,4,4a, 5,10,10a-hexahydroanthracene.
[0056]
Further, examples of the cyclic olefin represented by the above formula [I] or [II] include tricyclo [4.3.0.1 2,5 ] -3-decene and 2-methyltricyclo [4.3.0]. .1 2,5 ] -3-decene, 5-methyltricyclo [4.3.0.1 2,5 ] -3-decene and other tricyclos [4.3.0.1 2,5 ] -3- Decene derivatives, tricyclos such as tricyclo [4.4.0.1 2,5 ] -3-undecene, 10-methyltricyclo [4.4.0.1 2,5 ] -3-undecene [4.4. 0.1 2,5 ] -3-Undecene derivative,
[0057]
[化21]
[0058]
(In the above formula, the numbers 1 to 12 indicate the carbon position numbers.) And tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-hydrocarbon group have the derivatives substituted dodecene. Examples of the hydrocarbon group include 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, and 2,10. -Dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl , 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9- Methyl, 8-Ethylden-9-Ethyl, 8-Ethylden-9-Isopropyl, 8-Ethylden-9-Butyl, 8-n-Propyridene, 8-n-Propyridene-9-Methyl, 8-n-Propyridene-9- Ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene- 9-Isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl , 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl), 5 , 6-Diphenyl and the like.
[0059]
Further, examples of the cyclic olefin represented by the above formula [I] or [II] include an adduct of (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene, and pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 2, 5 . 1 9,12 . 0 8,13 ] -3-pentadecene and its derivatives, pentacyclo [6.5.1.1 3, 6 . 0 2,7 . 0 9,13 ] 4,10 penta octadecadienoic Penta cyclopentadiene octadecadienoic compounds such as pentacyclo [8.4.0.1 2, 5 . 1 9,12 . 0 8,13 ] -3-hexadecene and derivatives thereof, pentacyclo [6.6.1.1 3, 6 . 0 2,7 . 0 9,14 ] -4-hexadecene and derivatives thereof, hexacyclo [6.6.1.1 3,6 . 1 10, 13 . 0 2,7 . 0 9,14 ] -4-heptadecene and its derivatives, heptacyclo [8.7.0.1 2, 9 . 1 4, 7 . 1 11, 17.0 3,8 . 0 12,16 ] -5-eikosen and its derivatives, heptacyclo [8.8.0.1 2,9 . 1 4, 7 . 1 11, 18 . 0 3,8 . 0 12,17 ] -5- Heneikosen and its derivatives, Octacyclo [8.8.0.1 2,9 . 1 4, 7 . 1 11, 18 . 1 13, 16 . 0 3,8 . 0 12,17] -5-Docosen and its derivatives, nonacyclo [10.9.1.1 4,7 . 1 13, 20 . 1 15, 18 . 0 2,10 . 0 3,8 . 0 12, 21 . 0 14,19 ] -5-pentacosene and derivatives thereof, Nonashikuro [10.10.1.1 5,8 . 1 14, 21 . 1 16, 19.0 2,11 . 0 4,9 . 0 13, 22 . 0 15,20 ] -6-hexacosenoic and derivatives thereof.
[0060]
[化22]
[0061]
In the above formula [III], n and m are independently 0, 1 or 2, and q is 1, 2 or 3, respectively. m is preferably 0 or 1, more preferably 1. n is preferably 0 or 1, more preferably 0. q is preferably 1 or 2, more preferably 1.
R 18 to R 31 are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid. It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a group, an acid anhydride group, an epoxy group or an amino group, and R 18 to R 31 are independently hydrogen atoms or 1 to 20 carbon atoms, respectively. It is preferably a hydrocarbon group of, and more preferably a hydrogen atom.
Further, when q = 1, R 28 and R 29 , R 29 and R 30 , and R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q = 2 or 3, R may be formed. 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , and R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic ring may be formed. May have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.
[0062]
[化23]
[0063]
In the above formula [IV], q is 1, 2 or 3, preferably 1 or 2, and more preferably 1.
R 32 to R 39 are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid. It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a group, an acid anhydride group, an epoxy group or an amino group, and R 32 to R 39 are independently hydrogen atoms or 1 to 20 carbon atoms, respectively. It is preferably a hydrocarbon group of, and more preferably a hydrogen atom.
Further, when q = 1, R 36 and R 37 , R 37 and R 38 , and R 38 and R 39 may be combined with each other to form a monocyclic or polycyclic ring, and when q = 2 or 3, R may be formed. 36 and R 36 , R 36 and R 37, R 37 and R 38 , R 38 and R 39 , R 39 and R 39 may be coupled to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic has a double bond. The monocyclic ring or the polycyclic ring may be an aromatic ring.
[0064]
[化24]
[0065]
In the above formula [V], n and q are independently 0, 1 or 2, respectively. n is preferably 0 or 1, more preferably 0. q is preferably 0 or 1, more preferably 0.
R 1 to R 17 are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or halogen atom, carboxyl group, hydroxyl group, sulfonic acid. It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a group, an acid anhydride group, an epoxy group or an amino group, and one of R 10 to R 17 is a bonder, and R 15 is It is preferably a bonder.
R 1 to R 17 are preferably hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, respectively, and more preferably hydrogen atoms.
Also, when q = 0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 may be combined with each other to form a monocyclic or polycyclic ring, and when q = 1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16, R 16 and R 16 , R 16 and R 10 may be coupled to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic may have a double bond. The monocyclic ring or the polycyclic ring may be an aromatic ring.
Among the above formula [V], the compound represented by the following formula [V-1A] is preferable.
[0066]
[化25]
[0067]
In the above formula [V-1A], n is 0, 1 or 2. n is preferably 0 or 1, more preferably 0. Further, in the above formula [V-1A], R 1 to R 14 are independently hydrogen atom, halogen atom, carboxyl group, hydroxyl group, sulfonic acid group, acid anhydride group, epoxy group, amino group, or It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group or an amino group.
[0068]
Further, in the formulas [V] and [V-1A], the hydrocarbon groups having 1 to 20 carbon atoms are independently, for example, an alkyl group having 1 to 20 carbon atoms and a cyclo having 3 to 15 carbon atoms. Examples thereof include an alkyl group and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and examples of the cycloalkyl group include cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms, carboxyl groups, hydroxyl groups, sulfonic acid groups, acid anhydride groups or amino groups.
[0069]
The structural units derived from the cyclic olefin according to this embodiment are bicyclo [2.2.1] -2-heptene, bicyclo [2.2.1] -2-heptene derivative, and tetracyclo [4.4.0.1 2]. , 5 . 1 7,10 ] -3-dodecene, tetracyclo [4.4.0.1 2, 5 . 1 7, 10 ] -3-dodecene derivative, hexacyclo [6.6.1.1 3,6 . 1 10, 13 . 0 2,7 . 0 9,14 ] -4-heptadecene and hexacyclo [6.6.1.1 3,6 . 1 10, 13 . 0 2,7 . 0 9,14 ] -4-heptadecene derivatives, benzonorbornadiene, preferably contains a repeating unit derived from at least one compound selected from indene norbornene and methyl phenyl norbornene, bicyclo [2.2.1] -2 Heptene and tetracyclo [4.4.0.1 2,5 . 1 7, 10] -3-It is more preferable to contain a repeating unit derived from at least one compound selected from dodecene, and from the viewpoint of further improving the refractive index of the optical component according to the present embodiment, tetracyclo [4.4.0.1] 2,5 . 1 7,10 and even more preferably contains a repeating unit derived from] -3-dodecene.
[0070]
Specific examples of the cyclic olefins represented by the above formulas [I] [II] [III] [IV] or [V] are shown above, but more specific structural examples of these compounds are described in JP-A-6. Structural examples of cyclic olefins shown in paragraph numbers [0038] to [0058] of No. 228380, and structural examples of cyclic olefins shown in paragraph numbers [0027] to [0029] of JP-A-2005-330465. Examples of the structure of the cyclic olefin shown in paragraph numbers [0032] to [0054] of JP-A-7-145213 can be mentioned. The random copolymer (A1) according to the present embodiment may contain two or more units derived from the cyclic olefin.
[0071]
The cyclic olefin represented by the above formulas [I] [II] [III] [IV] or [V] can be produced, for example, by subjecting cyclopentadiene to an olefin having a corresponding structure by a Diels-Alder reaction. can.
[0072]
In the random copolymer (A1) according to the present embodiment, at least a part of the cyclic olefin represented by the above formula [I] [II] [III] [IV] or [V] is the following formula [VI] [VII]. [VIII] [IX] or [X] is considered to constitute a repeating unit.
[0073]
[化26]
[0074]
In the above formula [VI], n, m, q, R 1 to R 18 , Ra and R b have the same meaning as the above formula [I].
[0075]
[化27]
[0076]
In the above formula [VII], n, m, p, q and R 1 to R 19 have the same meaning as the above formula [II].
[0077]
[化28]
[0078]
In the above formula [VIII], n, m, q and R 18 to R 31 have the same meaning as the above formula [III].
[0079]
[化29]
[0080]
In the above formula [IX], q and R 32 to R 39 have the same meaning as the above formula [IV].
[0081]
[化30]
[0082]
In the above formula [X], n, q and R 1 to R 17 have the same meaning as the above formula [V].
[0083]
The cyclic olefin-based copolymer of the present embodiment contains [A-1] α-olefin having 2 to 20 carbon atoms and the above formulas [I], [II], [III], [IV] or [V]. [A-2] A ring-opening polymer or co-polymer of the cyclic olefin represented by the above formulas [I], [II], [III], [IV] or [V]. Polymer, [A-3] hydride of the ring-opening polymer or copolymer [A-2], [A-4] of the above [A-1], [A-2] or [A-3]. It is preferable to contain one or more selected from the graft modified products. From the viewpoint of improving the heat resistance and dimensional stability of the obtained optical component, the cyclic olefin-based copolymer of the present embodiment preferably contains a repeating unit derived from an α-olefin having 2 to 20 carbon atoms. , [A-1] A random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the above formulas [I], [II], [III], [IV] or [V]. It is more preferable to include.
[0084]
The above-mentioned random copolymer has the above-mentioned formula [I], [II], [III], [IV] or [V] when the total of all the constituent units constituting the above-mentioned random copolymer is 100 mol%. The content of the structural unit derived from the cyclic olefin shown is preferably 10 mol% or more and 60 mol% or less, and more preferably 20 mol% or more and 50 mol% or less.
The transparency of the optical component obtained when the content of the structural unit derived from the cyclic olefin represented by the above formulas [I], [II], [III], [IV] or [V] is not more than the above lower limit value. Etc. can be improved. Further, the optical component obtained by the content of the structural unit derived from the cyclic olefin represented by the above formula [I], [II], [III], [IV] or [V] is not more than the above upper limit value. Heat resistance and dimensional stability can be improved.
[0085]
The glass transition temperature of the cyclic olefin copolymer (A) according to the present embodiment is preferably 110 ° C. to higher from the viewpoint of further improving heat resistance while maintaining good transparency and refractive index of the obtained optical component. It is 200 ° C., more preferably 115 ° C. to 190 ° C., and even more preferably 120 ° C. to 180 ° C.
[0086]
The intrinsic viscosity [η] (in 135 ° C. decalin) of the cyclic olefin copolymer (A) according to the present embodiment is, for example, 0.05 to 5.0 dl / g, preferably 0.2 to 4.0 dl. / G, more preferably 0.3 to 2.0 dl / g, and particularly preferably 0.4 to 2.0 dl / g.
When the ultimate viscosity [η] is at least the above lower limit value, the mechanical strength of the obtained molded product can be improved. Further, when the ultimate viscosity [η] is not more than the above upper limit value, the moldability of the cyclic olefin resin composition according to the present embodiment can be improved.
[0087]
The cyclic olefin copolymer (A) according to the present embodiment preferably contains a polar group-containing cyclic olefin copolymer (Aa) containing a structural unit (a3) derived from a monomer having a polar group. The polar group is preferably one or more selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group and an amino group. Further, the structural unit (a3) derived from the monomer having a polar group is preferably located inside the main chain or the side chain of the polymer chain of the cyclic olefin copolymer (A). The cyclic olefin copolymer (A), which is a matrix, has the above polar groups inside the main chain or side chains of the polymer chain, and the interaction between the polar groups and the inorganic fine particles (B) causes the matrix. The dispersibility of the inorganic fine particles (B) in the inside can be improved. This makes it possible to realize higher transparency and a higher refractive index in the obtained optical component.
[0088]
Further, from the viewpoint of solvent resistance and abrasion resistance when a molded product is prepared using the cyclic olefin resin composition according to the present embodiment, the cyclic olefin copolymer according to the present embodiment ( A) preferably has the above-mentioned polar group. Since the cyclic olefin copolymer (A) according to the present embodiment has the above-mentioned polar group, a molded product was prepared using the cyclic olefin resin composition containing the cyclic olefin copolymer (A). The reason why the solvent resistance and the abrasion resistance are improved is not always clear, but the modifier that modifies the cyclic olefin copolymer (A) and the inorganic fine particles (B) forms a network. It is inferred that.
[0089]
The content of the structural unit (a3) derived from the monomer having the polar group in the polar group-containing cyclic olefin copolymer (Aa) is dispersed in the matrix of the cyclic olefin copolymer (A). From the viewpoint of improving the properties and further improving the transparency of the obtained optical component, when the total of all the structural units constituting the polar group-containing cyclic olefin-based copolymer (Aa) is 100 mol%. , 0.1 mol% or more, more preferably 0.2 mol% or more, further preferably 0.5 mol% or more, and the refractive index and moisture resistance of the obtained optical component. From the viewpoint of further improving the heat resistance, it is preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and 2 mol% or less. Especially preferable.
[0090]
The polar group-containing cyclic olefin copolymer (Aa) is obtained by grafting a random copolymer (A1) of a monomer having a polar group and a cyclic olefin and a monomer having a polar group onto the cyclic olefin polymer. Alternatively, it preferably contains one or more selected from the graft-polymerized graft copolymer (A2).
Here, "graft" means introducing a monomer having a polar group into a stem polymer which is a main chain. "Graft-polymerized" means introducing a branch polymer composed of a polymer different from the main chain into the stem polymer which is the main chain.
[0091]
The polar group-containing cyclic olefin copolymer (Aa) is a structural unit (a1) derived from an α-olefin having 2 to 20 carbon atoms, and the above formula [I]. , [II], [III], [IV] or [V], a random copolymer (A1) having a structural unit (a2) derived from a cyclic olefin and a structural unit (a3) derived from a monomer having a polar group. ) Is preferably included.
[0092]
The α-olefin having 2 to 20 carbon atoms according to this embodiment may be linear or branched. Examples of such α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. , 1-Eikosen and other linear α-olefins having 2 to 20 carbon atoms; 4-methyl-1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene and the like having carbon atoms Examples thereof include 4 to 20 branched α-olefins. Among these, a linear α-olefin having 2 to 4 carbon atoms is preferable, and ethylene is particularly preferable. The α-olefin-derived structural unit (a1) in the random copolymer (A1) preferably contains a repeating unit derived from ethylene. Such α-olefins may be used alone or in combination of two or more.
[0093]
When the total of all the structural units constituting the random copolymer (A1) according to the present embodiment is 100 mol%, the content of the structural unit (a1) derived from the α-olefin is preferably 30 mol% or more. It is 88 mol% or less, more preferably 40 mol% or more and 78 mol% or less.
When the content of the structural unit (a1) derived from the α-olefin is at least the above lower limit value, the heat resistance and dimensional stability of the obtained optical component can be improved. Further, when the content of the constituent unit (a1) derived from the α-olefin is not more than the above upper limit value, the transparency of the obtained optical component can be improved.
[0094]
When the total of all the structural units constituting the random copolymer (A1) according to the present embodiment is 100 mol%, the content of the structural unit (a1) derived from the α-olefin is preferably 30 mol% or more. It is 88 mol% or less, more preferably 40 mol% or more and 78 mol% or less.
When the content of the structural unit (a1) derived from the α-olefin is at least the above lower limit value, the heat resistance and dimensional stability of the obtained optical component can be improved. Further, when the content of the constituent unit (a1) derived from the α-olefin is not more than the above upper limit value, the transparency of the obtained optical component can be improved.
[0095]
The cyclic olefin-derived structural unit (a2) according to the present embodiment has an alicyclic structure and is a cyclic olefin-derived structural unit represented by the above formulas [I] [II] [III] [IV] or [V]. Is preferable.
[0096]
Specific examples of the cyclic olefin represented by the above formulas [I] [II] [III] [IV] or [V] are also as described above, and the structural unit derived from the cyclic olefin in the random copolymer (A1). (A2) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 2,5 . 1 7,10 and particularly preferably contains a repeating unit derived from] -3-one
[0097]
The structural unit (a3) derived from the polar group-derived monomer according to the present embodiment is derived from a monomer having at least one polar group selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group and an amino group. It is preferably a structural unit of the structural unit.
The monomer having a polar group is not particularly limited as long as it is a monomer having the above polar group, and examples thereof include a monomer represented by the following formula (10).
CH 2 = CH-R 1- Xp (10) In the
above equation (10), p is a positive integer of 1 or more and 3 or less, preferably 1.
R 1 is a hydrocarbon group having 0 or more carbon atoms, preferably a hydrocarbon group having 2 or more carbon atoms, more preferably a hydrocarbon group having 3 or more carbon atoms and 20 or less carbon atoms, and more preferably a hydrocarbon group having 5 or more carbon atoms and 15 or less carbon atoms.
X is at least one polar group selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group and an amino group, and more preferably selected from a carboxyl group, a hydroxyl group and an acid anhydride group. It is at least one polar group, more preferably at least one polar group selected from a carboxyl group and a hydroxyl group.
[0098]
Specific examples of the monomer having a polar group include a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, and an epoxy among the compounds described on pages 11 to 17 of JP-A-2-51510. Examples thereof include compounds having at least one polar group selected from a group and an amino group.
The monomers having these polar groups may be used alone or in combination of two or more.
Among these, from the viewpoint of excellent copolymerizability with cyclic olefins, acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptene acid, 7-octene acid, 8-nonenic acid, 9 -Decenoic acid, 10-undecenoic acid (undecylene acid), 11-dodecenoic acid, 2-propen-1-ol, 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, It preferably contains at least one selected from 6-heptene-1-ol, 7-octene-1-ol, 8-nonen-1-ol, undecenol and 11-dodecene-1-ol, preferably acrylic acid, 4-. It is more preferable to contain at least one selected from pentenic acid, 6-heptene acid, 9-decenoic acid, 10-undecenol and undecylene acid, and particularly preferably to contain at least one selected from 10-undecenol and undecylene acid. ..
[0099]
In the random copolymer (A1) according to the present embodiment, when the total of all the structural units constituting the random copolymer (A1) is 100 mol%, the structural unit (a3) derived from the monomer having a polar group The content is preferably 0.1 mol% or more, preferably 0.1 mol% or more, from the viewpoint of improving the dispersibility of the random copolymer (A1) in the matrix and further improving the transparency of the obtained optical component. It is more preferably 2 mol% or more, further preferably 0.5 mol% or more, and 20 mol% or less from the viewpoint of further improving the refractive index, moisture resistance, and heat resistance of the obtained optical component. It is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less.
[0100]
The random copolymer (A1) according to the present embodiment includes an α-olefin having 2 to 20 carbon atoms, a cyclic olefin represented by the above formulas [I] [II] [III] [IV] or [V], and a cyclic olefin represented by the above formula [I] [II] [III] [IV] or [V]. Using the above-mentioned monomer having a polar group, for example, it can be produced by the production method described in JP-A-2-51510, Patent No. 3817015, and Patent No. 5594712.
[0101]
The polar group-containing cyclic olefin copolymer (Aa) is represented by the above formulas [I], [II], [III], [IV] or [V]. It is preferable to include a graft copolymer (A2) obtained by grafting or graft-polymerizing a monomer having a polar group to a cyclic olefin-based polymer having a structural unit (a2) derived from a cyclic olefin. Further, the cyclic olefin-based polymer having the structural unit (a2) derived from the cyclic olefin is the ring-opening of the cyclic olefin represented by the above formulas [I], [II], [III], [IV] or [V]. It may be a polymer, or it may be a random α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the above formulas [I], [II], [III], [IV] or [V]. It may be a copolymer.
[0102]
As the cyclic olefin represented by the above formulas [I], [II], [III], [IV] or [V], the same one as the α-olefin described in the above random copolymer (A1) shall be used. Can be done. Therefore, the description thereof is omitted here.
The structural unit (a2) derived from the cyclic olefin in the graft copolymer (A2) is bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.1 2,5 . It is particularly preferred to include repeating units derived from one or more compounds selected from 17,10 ] -3-dodecene.
[0103]
When the total of all the structural units constituting the graft copolymer (A2) according to the present embodiment is 100 mol%, the content of the structural unit (a2) derived from the cyclic olefin is preferably 10 mol% or more and 60. It is mol% or less, more preferably 20 mol% or more and 50 mol% or less.
When the content of the cyclic olefin-derived structural unit (a2) is at least the above lower limit value, the transparency of the obtained optical component can be improved. Further, when the content of the structural unit (a2) derived from the cyclic olefin is not more than the above upper limit value, the heat resistance and dimensional stability of the obtained optical component can be improved.
[0104]
The graft copolymer (A2) preferably further has a structural unit (a1) derived from an α-olefin having 2 to 20 carbon atoms.
As the α-olefin having 2 to 20 carbon atoms, the same α-olefin as the α-olefin described in the above random copolymer (A1) can be used. Therefore, the description thereof is omitted here.
When the total of all the structural units constituting the graft copolymer (A2) according to the present embodiment is 100 mol%, the content of the structural unit (a1) derived from the α-olefin is preferably 30 mol% or more. It is 88 mol% or less, more preferably 40 mol% or more and 78 mol% or less.
When the content of the structural unit (a1) derived from the α-olefin is at least the above lower limit value, the heat resistance and dimensional stability of the obtained optical component can be improved. Further, when the content of the constituent unit (a1) derived from the α-olefin is not more than the above upper limit value, the transparency of the obtained optical component can be improved.
[0105]
In the graft copolymer (A2) according to the present embodiment, the structural unit (a3) derived from the monomer having a polar group is selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an acid anhydride group, an epoxy group and an amino group. It is a structural unit derived from a monomer having at least one polar group.
The monomer having a polar group in the graft copolymer (A2) according to the present embodiment is not particularly limited as long as it is a monomer having the above polar group, but for example, the polar group described in the above random copolymer (A1). Examples thereof include a monomer having the above, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like.
The monomers having these polar groups may be used alone or in combination of two or more.
Among these, it is preferable to contain at least one selected from acrylic acid, methacrylic acid, maleic acid and maleic anhydride from the viewpoint of ease of grafting to the cyclic olefin polymer.
[0106]
In the graft copolymer (A2) according to the present embodiment, when the total of all the structural units constituting the graft copolymer (A2) is 100 mol%, the structural unit (a3) derived from the monomer having a polar group The content is preferably 0.1 mol% or more, preferably 0, from the viewpoint of improving the dispersibility of the graft copolymer (A2) in the matrix and further improving the transparency of the obtained optical component. It is more preferably 2 mol% or more, further preferably 0.5 mol% or more, and 20 mol% or less from the viewpoint of further improving the refractive index, moisture resistance and heat resistance of the obtained optical component. It is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less.
[0107]
The graft copolymer (A2) according to the present embodiment is different from, for example, a cyclic olefin polymer produced by the production method described in JP-A-5-320258, JP-A-7-13084, etc. It can be obtained by grafting or graft-polymerizing a monomer having the above polar group by the method described in Kai 2016-056318, WO2008 / 059938, WO2010 / 050437 and the like.
[0108]
(Inorganic Fine Particles (B))
The cyclic olefin resin composition according to the present embodiment contains inorganic fine particles (B) whose surface is modified with a modifier, and the modifiers are phosphoric acid ester, organic phosphonic acid, and phosphonic acid. One or more selected from the group consisting of esters, carboxylic acids, sulfonic acids, hydrocarbon compounds having an amino group, and silane coupling agents.
[0109]
The modifier is preferably a compound represented by the following formula (1).
R 1- X (1)
[0110]
In the above formula (1), R 1 represents a hydrocarbon group having 3 to 18 carbon atoms. Examples of the hydrocarbon group having 3 to 18 carbon atoms include a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, and a hydrocarbon group having an alicyclic structure. Examples thereof include a hydrocarbon group having an aromatic ring structure. From the viewpoint of obtaining a resin composition having excellent transparency by particularly improving the dispersibility of the modified inorganic particles in the cyclic olefin-based copolymer (A), among these, a chain-like structure that does not contain a ring structure. The hydrocarbon group having 3 to 18 carbon atoms is preferable, the linear hydrocarbon group having 3 to 18 carbon atoms is more preferable, and the linear hydrocarbon group having 12 to 18 carbon atoms is particularly preferable.
[0111]
X represents a functional group that forms a bond with the surface of the inorganic fine particles (B) or an atomic group having the functional group.
When the modifier has a functional group that forms a bond with the surface of the inorganic fine particles (B), these groups are condensed with a functional group existing on the surface of the inorganic particles (for example, a hydroxyl group or a mercapto group). A reaction occurs and its surface is modified with a modifier.
[0112]
Here, examples of the functional group that forms a bond with the surface of the inorganic fine particles (B) include a hydroxyl group, a carboxyl group, a hydrohydroxyphosphoryl group, a phosphono group, a sulfino group, a sulfo group, a hydrolyzable group such as a ticoxy group, and the like. Can be mentioned.
[0113]
Further, examples of the atomic group having a functional group that forms a bond with the surface of the inorganic particles include atomic groups represented by the following formulas (2) to (4).
[0114]
[化31]
[0115]
In formulas (2) to (4), Y represents a hydroxyl group or a hydrolyzable group, and Z 1 and Z 2 are independently hydrogen atoms, hydroxyl groups, hydrocarbon groups having 1 to 18 carbon atoms, or carbon numbers. Represents 1 to 18 hydrocarbon oxy groups. * Represents a bond with R 1 .
[0116]
Examples of the hydrocarbon group having 1 to 18 carbon atoms of Z 1 and Z 2 include a group represented by R 1 ; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a vinyl group, an allyl group, a phenyl group and the like. A hydrocarbon group having 1 to 18 carbon atoms; and the like. The hydrocarbon oxy group having 1 to 18 carbon atoms of
Z 1 and Z 2 is a group represented by −OR 1 ; having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a vinyloxy group, an allyloxy group and a phenoxy group. Hydrocarbon oxy group; etc.
[0117]
Further, in order to satisfactorily disperse the modified inorganic particles in the transparent resin, it is preferable that the modifying agent modifies the inorganic particles in a two-conformation or a tri-conformation. Therefore, it is more preferable that Z 1 in the formulas (2) to (4) is a hydrogen atom or a hydroxyl group.
[0118]
Specific examples of the compounds used as modifiers in the present embodiment include butanoic acid, hexane acid, phosphonic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecane. Acids, oleic acid, linoleic acid, cyclohexanecarboxylic acid, 1-adamantancarboxylic acid, dodecenyl phosphate, tridecenyl phosphate, tetradecenyl phosphate, pentadecenyl phosphate, hexadecenyl phosphate, heptadecenyl phosphate, octadecenyl phosphate, oleyl phosphate, Phosphonates such as octadecadienyl phosphate, octadecatelyl phosphate, diorail phosphate; dodecenylphosphonic acid, tridecenylphosphonic acid, tetradecenylphosphonic acid, pentadecenylphosphonic acid, Organic phosphonic acids such as hexadecenylphosphonic acid, heptadecenylphosphonic acid, octadecenylphosphonic acid, oleylphosphonic acid, octadecadienylphosphonic acid, octadecatorienylphosphonic acid, dioleylphosphonic acid; Decenylphosphonate, tridecenylphosphonic acid, tetradecenylphosphonic acid, pentadecenylphosphonic acid, hexadecenylphosphonate, heptadecenylphosphonate, octadecenylphosphonate, oleylphosphonate Phosphonate esters such as; silane compounds such as dodecyltrimethoxysilane, octadecyltrimethoxysilane, dodecenyltrimethoxysilane, pentadecenyltrimethoxysilane; and the like.
The compounds used as modifiers can be used alone or in combination of two or more.
[0119]
The modifier preferably contains one or more selected from a phosphoric acid ester and a carboxylic acid, and is a phosphoric acid ester containing a hydrocarbon group having 12 to 18 carbon atoms and a hydrocarbon group having 12 to 18 carbon atoms. It is particularly preferable to contain one or more selected from carboxylic acids containing. Contains one or more selected from the cyclic olefin copolymer (A), a phosphoric acid ester containing a hydrocarbon group having 12 to 18 carbon atoms, and a carboxylic acid containing a hydrocarbon group having 12 to 18 carbon atoms. By including the inorganic fine particles (B) modified with the modifier, the dispersibility of the inorganic fine particles (B) in the matrix can be further improved by the interaction between the two.
[0120]
The inorganic fine particles (B) according to the present embodiment are not particularly limited as long as they are finely dispersed in the matrix of the cyclic olefin copolymer (A), but are excellent in the effect of improving the refractive index of the obtained optical component. From, zirconia; titania; alumina; oxides or nitrides such as Zr, Ti, Hf, Al, Zn and lanthanoids; oxides or nitrides of composite metals; and the like. Of these, zirconia, titania and alumina are preferable. These may be used alone or in combination of two or more. Among these, zirconia and titania are preferable from the viewpoint of being more excellent in the effect of improving the refractive index, and a viewpoint capable of preventing deterioration of the cyclic olefin copolymer (A), particularly the polar group-containing cyclic olefin copolymer (A). Therefore, zirconia is more preferable.
[0121]
The average particle diameter D 50 of the inorganic fine particles (B) is 100 nm or less from the viewpoint of improving the dispersibility of the cyclic olefin copolymer (A) in the matrix and further improving the transparency of the obtained optical component. Is more preferable, 80 nm or less is more preferable, 60 nm or less is further preferable, and 20 nm or less is particularly preferable.
The average particle diameter D 50 of the inorganic fine particles (B) is not particularly limited, but is, for example, 1 nm or more.
The average particle through D of the inorganic fine particles (B) 50 is, for example, can be measured by a dynamic light scattering method.
[0122]
The method for producing the inorganic fine particles (B) whose surface is modified with a modifier is not particularly limited, and can be obtained by, for example, the following method.
[0123]
First, an aqueous dispersion of the inorganic fine particles (B) obtained by dispersing the inorganic fine particles (B) in water is obtained. Subsequently, the aqueous dispersion of the inorganic fine particles (B) and the surface modifier are mixed. At this time, the surface modifier can be added by itself, or a surface modifier mixed with an organic solvent in advance can be added.
[0124]
Here, by adjusting the blending ratio of the inorganic fine particles (B) and the surface modifier, the modification amount of the modifier that modifies the surface of the inorganic fine particles (B) can be adjusted. The amount of the modifier that modifies the surface of the inorganic fine particles (B) is not particularly limited, but when the amount of the inorganic fine particles (B) is 100, it is preferably 20% by mass or more and 40% by mass or less, preferably 20% by mass. More preferably, it is% or more and 30% by mass or less.
By setting the modification amount of the modifier that modifies the surface of the inorganic fine particles (B) within the above numerical range, the dispersibility of the inorganic fine particles (B) in the matrix can be further improved, and the inorganic fine particles (B) can be dispersed. The effect of improving the refractive index by dispersing B) can be sufficiently obtained.
[0125]
Subsequently, water is removed from the obtained mixed solution containing the aqueous dispersion of the inorganic fine particles (B) and the surface modifier by an arbitrary method and replaced with an organic solvent. When water is removed by a rotary evaporator or the like, an organic solvent is added to a mixed solution containing an aqueous dispersion of inorganic fine particles (B) and a surface modifier obtained as needed, and the dispersion medium is removed by evaporation. By repeating the above steps, an inorganic fine particle (B) dispersion solution in which the inorganic fine particles (B) are dispersed in an organic solvent can be obtained.
[0126]
(Other Ingredients)
The cyclic olefin resin composition according to the present embodiment contains , if necessary, a phenol-based stabilizer, a higher fatty acid metal salt, an antioxidant, an ultraviolet absorber, a hindered amine-based light stabilizer, and hydrochloric acid absorption. Agents, metal deactivators, antistatic agents, antifogging agents, lubricants, slip agents, nucleating agents, plasticizers, flame retardants, phosphorus-based stabilizers, etc. can be blended to the extent that the object of the present invention is not impaired. , The compounding ratio is an appropriate amount.
[0127]
(Method for Preparing Cyclic Olefin Resin Composition) In the cyclic olefin resin composition according to the
present embodiment, the cyclic olefin copolymer (A) and the inorganic fine particles (B) are known from an extruder, a Banbury mixer and the like. It can be obtained by a method of kneading using a kneading device; a method of dissolving or dispersing the cyclic olefin copolymer (A) and the inorganic fine particles (B) in a common solvent, mixing them, and then evaporating the solvent. can.
Among these, from the viewpoint of further improving the transparency of the obtained optical component, the cyclic olefin copolymer (A) and the inorganic fine particles (B) are dissolved or dispersed in a common solvent and mixed, and then the solvent is added. The method of evaporating is preferable.
[0128]
[Molded article and optical component]
Next, the molded article according to the embodiment of the present invention will be described.
The molded product according to the present embodiment is molded using the cyclic olefin resin composition according to the present embodiment.
Since the molded product according to the present embodiment is composed of the cyclic olefin resin composition according to the present embodiment, it has transparency and a high refractive index. Therefore, it can be suitably used as an optical component in an optical system that needs to identify an image with high accuracy. Optical components are components used in optical equipment, etc., and specifically include sensor lenses such as eyeglass lenses, fθ lenses, pickup lenses, imaging lenses, and lenses used in image sensors, prisms, and projector lenses. Examples include a light guide plate and an in-vehicle camera lens. The optical component according to this embodiment can be particularly preferably used as an imaging lens.
[0129]
When the molded product according to the present embodiment is used for optical purposes, it is essential to transmit light rays, so that it is preferable that the light transmittance is good. The light transmittance is defined by the spectral light transmittance or the total light transmittance depending on the application.
[0130]
When it is expected to be used in all light rays or in a plurality of wavelength regions, it is necessary that the total light transmittance is good, and the total light transmittance is preferably 85% or more when the antireflection film is not provided on the surface. Is 88-93%. If the total light transmittance is 85% or more, the required amount of light can be secured. A known method can be applied to the method for measuring the total light transmittance, and the measuring device and the like are not limited. For example, the cyclic olefin resin composition according to the present embodiment is molded into a sheet having a thickness of 3 mm in accordance with ASTM D1003. Then, a method of measuring the total light transmittance of the sheet obtained by molding the cyclic olefin resin composition according to the present embodiment using a haze meter and the like can be mentioned.
[0131]
Further, in the case of an optical system used only in a specific wavelength range, for example, a laser optical system, even if the total light transmittance is not high, it can be used as long as the spectral light transmittance in the wavelength range is good. In this case, the spectral light transmittance at the wavelength used when the antireflection film is not provided on the surface is preferably 85% or more, more preferably 86% to 93%. When the spectral light transmittance is 85% or more, the required amount of light can be secured. Further, a known method can be applied as a measuring method and an apparatus, and a spectrophotometer can be specifically exemplified.
[0132]
Further, the molded product according to the present embodiment has excellent light transmittance of light having a wavelength of 450 nm to 800 nm.
When used as an optical component, the light transmittance can be further improved by providing a known antireflection film on the surface.
[0133]
The molded product according to the present embodiment can be used in various forms such as a spherical shape, a rod shape, a plate shape, a columnar shape, a tubular shape, a tubular shape, a fibrous shape, a film or a sheet shape.
The method for molding the cyclic olefin resin composition according to the present embodiment to obtain a molded product is not particularly limited, and a known method can be used. Depending on the application and shape, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding and the like can be applied. Is. Among these, the injection molding method is preferable from the viewpoint of moldability and productivity. The molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, the resin temperature in injection molding is usually 150 ° C. to 400 ° C., preferably 200 ° C. to 350 ° C., more preferably 230 ° C. to 330 ° C. It is appropriately selected in the range.
[0134]
Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.
Example
[0135]
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
[0136]
(Cyclopentadienyl) Titanium (di-t-butylketimid) dichloride (CpTiNCtBu 2 Cl 2 ) was synthesized in accordance with Japanese Patent No. 4245801.
[0137]
[Production Example 1] After
passing nitrogen as an inert gas at a flow rate of 100 NL / h for 30 minutes in a glass reaction vessel having a volume of 2000 ml equipped with a stirrer, cyclohexane (cyclohexane, tetracyclo [4.4.0.1 2, 5 .1 7,10 ]-3-dodecene and the amount the sum of undecylenic acid is 1000 ml), tetracyclo [4.4.0.1 2, 5 .. 1 7,10 ] -3-dodecene (hereinafter, also referred to as tetracyclododecene.) And undecylenic acid was further added at a ratio shown in Table 1, a toluene solution of triisobutyl aluminum (26.4 mmol, concentration 1.0mM / ML) was added. Then, the solvent temperature was raised to 50 ° C. while stirring the polymerization solvent at a rotation speed of 600 rpm. After the solvent temperature reaches a predetermined temperature, the flowing gas is switched from nitrogen to ethylene, ethylene is circulated in the reaction vessel at a supply rate of 100 NL / h, and after 10 minutes have passed, (cyclopentadienyl) titanium (di) is used. A toluene solution reaction of -t-butylketimid) dichloride in a toluene solution (0.040 mmol) and methylaluminoxane (12 mmol) in a toluene solution was added to a glass reaction vessel to initiate polymerization.
After 20 minutes, 5 ml of methanol and acetylacetic acid were added in an amount of 20 equivalents with respect to the aluminum concentration to terminate the polymerization, and a polymerization solution containing a copolymer of ethylene, tetracyclododecene and undecylenic acid was obtained. .. Then, 500 ml of a 1.0 mol / L hydrochloric acid aqueous solution was added to the reaction vessel, and the mixture was stirred at 50 ° C. for 1 hour at 600 rpm. After separating the oil layer and the aqueous layer, the oil layer was added to a beaker containing about 3 times the volume of acetone under stirring to precipitate a copolymer, and the precipitated copolymer was separated from the filtrate by filtration. When the obtained polymer containing the solvent was dried under reduced pressure at 130 ° C. for 10 hours, a white powdery ethylene / tetracyclolodecene / undecylene acid copolymer (cyclic olefin copolymer containing a polar group (cyclic olefin copolymer). A-1)) 3.79 g was obtained.
[0138]
[Table 1]
[0139]
[Production Example 2]
APL6015T (manufactured by Mitsui Chemicals, Inc.), 1.5 parts by mass of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and t-butylperoxybenzoate (manufactured by Nippon Oil & Fats Co., Ltd., trade name Perbutyl Z) A solution in which 1.5 parts by mass was dissolved in acetone was blended. Then, using a twin-screw kneader (manufactured by Technobel Co., Ltd., KZW15), melt modification was performed at a resin temperature of 250 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 25 g / min. Upon extrusion, the radical initiator, solvent and unreacted maleic anhydride were evacuated. The extruded molten strand was pelletized after cooling to obtain a cyclic olefin copolymer (A-2) containing a polar group.
[0140]
Surface-modified zirconia surface-modified
with butyric acid, lauric acid, palmitic acid, and dodecyl phosphate was produced by the following method.
In a 200 mL eggplant flask set with a stirrer chip, take various hydrophobized surface modifiers in an amount corresponding to 23% by mass with respect to the zirconia to be treated, and use 42 mL of toluene as a water-insoluble organic solvent and an amphoteric organic solvent. To a certain methanol (30 mL) was added, 3 mL of a zirconia fine water dispersion (zirconia content: 30% by mass) was added and mixed. As the zirconia fine particle aqueous dispersion, Sakai Chemical Industry Co., Ltd. (SZR-W) was used. In the obtained mixed solution, toluene and water, which are water-insoluble organic solvents, are dissolved in methanol, which is an amphoteric organic solvent, to form a uniform liquid phase, and white turbidity, which is considered to be caused by zirconia fine particles, is generated. rice field.
[0141]
The mixture obtained above was stirred at room temperature for 1 hour, and then the dispersion medium was evaporated and removed by a rotary evaporator until the amount became about 3 to 5 mL. Evaporation and removal of the dispersion medium was carried out by reducing the pressure of the atmosphere to such a pressure that bumping in the liquid phase did not occur while keeping the mixed solution at room temperature.
[0142]
The mixed solution remaining in the eggplant flask after the first evaporation and removal of the dispersion medium had cloudiness, and the liquid phase was separated into two phases. Further, 30 mL of methanol and 42 mL of toluene were added to the mixed solution to make a cloudy dispersion having no interface again, and the operation of evaporation was performed again until the amount became about 3 to 5 mL. By repeating this operation approximately several times, the dispersion liquid could be changed from a cloudy state to a colorless and transparent state depending on the type and amount of the surface modifier used, and the remaining liquid phase could be made a single phase. In this example, the mixed solvent of water / methanol / toluene was replaced with a solvent containing only toluene to obtain a toluene dispersion of zirconia fine particles by 5 to 6 operations.
Toluene was removed from the toluene dispersion of zirconia fine particles by evaporation and then vacuum dried at 25 ° C. for 24 hours to obtain white solid zirconia fine particles. The obtained zirconia fine particles were redispersed in toluene, and the particle size was measured by dynamic light scattering (DLS). The average particle size of the lauric acid-modified zirconia fine particles was 18.4 nm.
[0143]
A
cyclic olefin polymer / zirconia nanoparticle composite film was prepared by the following method. In addition, various physical properties were measured or evaluated by the following methods. The results obtained are shown in Table 2.
[Preparation of Cyclic Olefin Polymer / Zirconia Nanoparticle Composite Film]
Cyclic olefin polymers A-1 and A-2 synthesized in Production Examples 1 and 2 and APL6509T manufactured by Mitsui Chemicals, Inc. (containing polar groups). Each of the cyclic olefin-based copolymers A-3) was dissolved in cyclohexane to prepare 5% by mass solutions. Then, a 5% by mass cyclohexane solution prepared by using the surface-modified zirconia surface-modified with butanoic acid, lauric acid, palmitic acid, and dodecylphosphate obtained by the above method was added to the polymer with zirconia nanoparticles. The mixture was added so as to have the ratio shown in Table 2, and the mixture was stirred with a magnetic stirrer at room temperature for 1 hour, allowed to flow on a glass plate, and bar-coated. After drying at 25 ° C. for 24 hours, the solvent was removed by vacuum drying at 80 ° C. for 15 hours to obtain a cyclic olefin polymer / zirconia nanoparticle composite film having a film thickness of 100 μm.
[0144]
[Total light transmittance] The
total light transmittance was measured based on JIS K-7105 using a double beam type haze computer HZ-2 manufactured by Suga Test Instruments Co., Ltd., and evaluated according to the following criteria.
Evaluation of total light transmittance
◎: 90% or more
○: 80% or more and less than 90%
×: less than 80%
[0145]
[Glass transition temperature Tg (° C.)] Measured under
an N 2 (nitrogen) atmosphere using DSC-6220 manufactured by Shimadzu Science Co., Ltd. The temperature was raised from room temperature to 200 ° C. at a heating rate of 10 ° C./min and then held for 5 minutes, and then the temperature was lowered to −20 ° C. at a temperature lowering rate of 10 ° C./min and then held for 5 minutes. Then, the glass transition temperature (Tg) of the polar group-containing cyclic olefin copolymer was determined from the heat absorption curve when the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min.
[0146]
[Refractive index]
The refractive index (nD) at a wavelength of 589 nm was measured using a refractive index / film thickness measuring device (Prism Coupler Model 2010 / M manufactured by Metricon Co., Ltd.).
[0147]
[Evaluation of Solvent Resistance (Toluene)]
0.3 g of the cyclic olefin polymer / zirconia nanoparticle composite film having a thickness of 100 μm obtained in Examples and Comparative Examples was placed in a flask and weighed (Y (Y). g)), toluene was added so as to form a 1% by mass solution, and the mixture was immersed at 25 ° C. for 24 hours. The insoluble matter was captured by filtering with a membrane filter (pore diameter 10 μm), dried at 25 ° C. for 48 hours, and then the mass (Z (g)) of the insoluble matter was measured. The insoluble fraction was calculated according to the following formula and evaluated according to the following criteria.
Insoluble fraction (mass%) = (Z / Y) × 100
Evaluation of insoluble fraction (mass%)
○: Insoluble fraction ≥ Zirconia content (mass%)
×: Insoluble fraction