Curable resin composition, cured article, and optical waveguide

Abstract

The purpose of the present invention is to provide a curable resin composition which enables the formation of a cured article that is small in absorption (low optical absorption loss) in a near-infrared region that has been employed in optical communication, is excellent in heat resistance, and has a low refractive index. This curable resin composition is characterized by comprising: a polysiloxane resin (A) having one or more reactive groups selected from the group consisting of a (meth)acryloyl group and a styryl group and also having an organic group containing a fluorine atom; a (meth)acrylic acid derivative (B) containing no fluorine atom and having a structure represented by general formula (1) and / or a (meth)acrylic acid derivative (B) containing a fluorine atom and having a structure represented by general formula (2), wherein general formulae (1) and (2) are described in the description; and a radical polymerization initiator (C).

Description

Curable resin composition, cured product and optical waveguide

[0001] The present invention relates to a curable resin composition (hereinafter sometimes abbreviated as "resin") useful as an optical waveguide, an optical adhesive, a transparent sealant, or a related part thereof that can be used in optical applications, such as optical communication applications and optical integrated circuit applications; a cured product obtained by curing the curable resin composition; and an optical waveguide comprising the cured product.

[0002] In recent years, there has been an ever-increasing demand for faster and higher capacity communications and signal transmission. Optical signal transmission, instead of electrical, is also becoming increasingly important in the internal wiring of devices. This short-distance optical communication technology is called optical interconnect, and active development is underway on optical-electronic composite boards, which replace some of the copper electrical wiring on printed circuit boards with optical wiring using optical fiber or optical waveguides.

[0003] Required properties of materials used in optical waveguides include low absorption in the near-infrared region used in optical communications, adjustable refractive index, excellent heat resistance, and excellent productivity. Traditionally, silica-based materials have been commonly used as materials for optical waveguides, but in recent years, there has been active research into optical waveguides made from polymer materials, which are low-cost and easy to process.

[0004] For example, fluorinated polyimides that can be used as optical materials for optical waveguides have been reported (Patent Document 1). However, although fluorinated polyimide-based materials have few CH groups in the molecule and have low absorption in the near-infrared region, they have problems such as cracking due to stress caused by the difference in linear expansion coefficient between the substrate and the film because they require baking at high temperatures, and reduced productivity due to the increased number of steps required for reactive ion etching to perform patterning.

[0005] An organic / inorganic hybrid material having an organic reactive group and a siloxane skeleton has been reported as a material that can be patterned by photolithography and does not produce by-products (Patent Document 2). However, its absorption in the near-infrared region is not sufficiently small, and further improvement is required.

[0006] Light-emitting and receiving elements that transmit and receive light via optical waveguides in optoelectronic composite substrates are typically sealed with transparent optical adhesives to enhance the reliability of the elements. For example, optical adhesives are used to connect light-emitting and receiving elements such as vertical cavity surface-emitting lasers (VCSELs) to optical waveguides on the substrate, followed by reflow soldering to connect the light-emitting and receiving elements to electrical wiring and secure the elements in place. Therefore, such optical adhesives are required to have the same performance as materials used in optical waveguides.

[0007] Furthermore, when directly connecting an optical fiber to a silicon optical waveguide, it is desirable for the optical adhesive to have a refractive index as low as that of silica-based materials in order to reduce optical loss due to the difference in refractive index with the optical fiber. Therefore, such an optical adhesive is required to be transparent at the near-infrared wavelengths used in optical communications, and also to be able to adjust its refractive index to be as low as that of silica-based materials.

[0008] To solve these problems, for example, a resin composition containing a liquid aliphatic epoxy compound and a specific aromatic epoxy compound (Patent Document 3) and a curable resin composition containing a (meth)acrylic acid ester having an alicyclic hydrocarbon group (Patent Document 4) have been developed. However, the absorption and refractive index in the near-infrared region are not sufficiently small, and further improvements are required.

[0009] JP 5-1148 U.S. Patent No. 6,984,483 JP 2020-184091 JP 11-61081

[0010] An object of the present invention is to provide a curable resin composition that has low absorption (low optical absorption loss) in the near-infrared region used in optical communications, is excellent in heat resistance, and is capable of forming a cured product with a low refractive index; a cured product of the curable resin composition; and an optical waveguide including the cured product.

[0011] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that the above-mentioned problems can be solved by combining a specific polysiloxane resin, a specific (meth)acrylic acid derivative, and a radical polymerization initiator, thereby completing the present invention.

[0012] That is, the present invention is as follows: [1] A curable resin composition containing the following components (A) to (C): (A) a polysiloxane resin having one or more reactive groups selected from the group consisting of a (meth)acryloyl group and a styryl group, and an organic group containing a fluorine atom; (B) a (meth)acrylic acid derivative (B-1) containing no fluorine atom and having a structure represented by the following general formula (1), and / or a (meth)acrylic acid derivative (B-2) containing a fluorine atom and having a structure represented by the following general formula (2): (In the above general formula (1), R １ａ is a hydrogen atom or a methyl group, and Y １ is a single bond, a methylene group, or an oxyethylene group; Z １ is any one of the following general formulas (1-1) to (1-6), and n represents 1 or 2. When n is 2, a plurality of R １ａ and Y １ may be the same or different.) (In the above general formulas (1-1) and (1-4), R ２ａ is a single bond, an oxygen atom, or a methylene group, and in the general formula (1-2), R ３ａ represents a hydrogen atom or a methyl group.) (In the above general formula (2), R １ｂ is a hydrogen atom or a methyl group, and Y ２ is a single bond, an alkylene group having 1 to 9 carbon atoms, or an alkylene group having 1 to 9 carbon atoms and containing a fluorine atom; Z ２ represents a single bond, a hydrogen atom, a fluorine atom, or any one of the following general formulae (2-1) to (2-8), and n represents 1 or 2. In the above general formula (2), Y ２ is a single bond or an alkylene group having 1 to 9 carbon atoms, Z ２ is a fluorine atom or any one of the following general formulae (2-1) to (2-8), and Y ２ is an alkylene group having 1 to 9 carbon atoms containing a fluorine atom, Z ２ is a single bond, a hydrogen atom, a fluorine atom, or any one of the following general formulae (2-1) to (2-8). When n is 2, a plurality of R １ｂ and Y２ may be the same or different.) (In the above general formulas (2-1) and (2-5), R ２ｂ is a single bond, an oxygen atom, or a methylene group, and in the general formula (2-2), R ３ｂ is a hydrogen atom or a methyl group. At least one of the hydrogen atoms constituting the aromatic ring in the general formulae (2-1) to (2-8) is a fluorine atom or CF ３ (C) Radical polymerization initiator

[0013] [2] The curable resin composition according to [1], wherein the mass ratio of the component (A) to the component (B) is 99:1 to 10:90.

[0014] [3] R in the general formula (1) １ａ is a hydrogen atom, and Y １ [3] The curable resin composition according to [1] or [2], wherein

[0015] [4] R in the general formulas (1-1) and (1-4) ２ａ and R in the general formulas (2-1) and (2-5) ２ｂ is a single bond or an oxygen atom.

[0016] [5] R in the general formula (1-2) ３ａ and R in the general formula (2-2) ３ｂ [5] The curable resin composition according to any one of [1] to [4], wherein is a hydrogen atom.

[0017] [6] The curable resin composition according to any one of [1] to [5], wherein the content of fluorine atoms in the component (A) is 1 to 24 mass%.

[0018] [7] The curable resin composition according to any one of [1] to [6], wherein the component (A) contains at least one of structures represented by the following general formulas (3) and (4): (In the above general formulas (3) and (4), R ４ is a fluorine atom or an organic group having 1 to 20 carbon atoms and containing one or more fluorine atoms, and in the above general formulas (4) and (5), R５ and R ６ each independently represents a methyl group or a phenyl group.

[0019] [8] The curable resin composition according to [7], wherein the component (A) further contains a structure represented by the following general formula (5), and the molar ratio of the structures represented by the general formulas (3) and (4) to the structure represented by the general formula (5) is 1:1 to 1:1.4: (In the above general formula (5), R ７ and R ８ each independently represents a methyl group or a phenyl group.

[0020] [9] A cured product obtained by curing the curable resin composition according to any one of [1] to [8].

[0021]

[10] An optical waveguide comprising the cured product according to [9].

[0022] According to the present invention, it is possible to provide a curable resin composition that has low absorption (low optical absorption loss) in the near-infrared region used in optical communications, has excellent heat resistance, and is capable of forming a cured product with a low refractive index.

[0023] The present invention will be described below, but the present invention is not limited by the examples in the following description. In this specification, the term "to" indicating a numerical range includes the upper and lower limits. In this specification, "A and / or B" is synonymous with "at least one of A and B." In other words, "A and / or B" means that it may be only A, only B, or a combination of A and B.

[0024] [Curable Resin Composition] The curable resin composition of the present embodiment contains (A) a polysiloxane resin, (B) a (meth)acrylic acid derivative, and (C) a radical polymerization agent as essential components.

[0025] <(A) Polysiloxane Resin> In this embodiment, the polysiloxane resin has one or more reactive groups selected from the group consisting of a (meth)acryloyl group and a styryl group, and an organic group containing a fluorine atom. In this specification, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

[0026] The polysiloxane resin may have at least one reactive group, and may have two or more, or may have three or more. For example, a (meth)acryloyl group as the reactive group is particularly excellent in UV curability, and a styryl group is particularly excellent in low light absorption loss, and is therefore preferred. The proportion of reactive groups may be selected appropriately depending on the desired physical properties, and any reactive group may be included alone or in combination, and is not particularly limited. From the viewpoint of improving UV curability, it is preferable for the polysiloxane resin to have two or more reactive groups. Furthermore, from the viewpoint of not leaving unreacted reactive groups, it is preferable for the number of reactive groups in a single molecular chain of the polysiloxane resin to be 10 or less.

[0027] In the polysiloxane resin, the concentration of reactive groups is preferably 500 to 10,000 mmol / kg, since sufficient curability can be obtained.

[0028] Furthermore, the polysiloxane resin has an organic group containing a fluorine atom. By having the polysiloxane resin have an organic group containing a fluorine atom, the refractive index can be reduced when the curable resin composition is cured.

[0029] Examples of the organic group containing a fluorine atom include groups in which some or all of the hydrogen atoms constituting the organic group have been substituted with fluorine atoms. From the viewpoint of compatibility, the number of carbon atoms in the organic group containing a fluorine atom is preferably 0 to 8, more preferably 0 to 6, and particularly preferably 0 to 3. When the number of carbon atoms in the organic group containing a fluorine atom is 0, it means that the group is a fluoro group. Specific examples of the organic group containing a fluorine atom include a fluoro group, a trifluoroethyl group, a trifluoropropyl group, a pentafluorophenyl group, a 1H,1H,2H,2H-nonafluorohexyl group, a 1H,1H,2H,2H-perfluoro-n-octyl group, a 1H,1H,2H,2H-perfluorodecyl group, a 5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl group, and a pentafluorophenyloxyalkyl group.

[0030] The content of fluorine atoms in the polysiloxane resin of this embodiment is preferably 1 to 24% by mass. A fluorine atom content of 1% by mass or more can reduce the refractive index. The fluorine atom content is more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more. The fluorine atom content in the polysiloxane resin can be measured by combustion ion chromatography analysis.

[0031] The polysiloxane resin of the present embodiment is not particularly limited as long as it has a siloxane skeleton, and examples thereof include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-butyltrimethoxysilane, iso-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-s Organotrialkoxysilanes such as styrylmethoxysilane, p-styrylethoxysilane, p-styryltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane; diorganodialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylcyclohexyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, and 3-(meth)acryloyloxypropylmethyldiethoxysilane;Various chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3-(meth)acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, and diphenyldichlorosilane, as well as tetraethoxysilane, tetramethoxysilane, diphenylsilanediol, di-p-tolylsilanediol, bis(4-ethylphenyl)silanediol, bis(4-isopropylphenyl)silanediol, dinasilanediol, ... phthalic anhydride, bis([1,1'-biphenyl]-4-yl)silanediol, trimethoxy(4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, (4-isopropenylphenyl)trimethoxysilane, trimethoxy(4-vinyl-1-naphthyl)silane, trimethoxy(4'-vinyl-[1,1'-biphenyl]-4-yl)silane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, trimethoxyfluorosilane Orosilane, triethoxyfluorosilane, pentafluorophenylmethoxydimethylsilane, pentafluorophenylethoxydimethylsilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, 11-pentafluorophenoxyundecyltrimethoxysilane, 11-pentafluorophenoxyundecyltriethoxysilane, 1H,1H,2H,2H-nonafluorohexyltrimethoxysilane, 1H,1H,2H,2H-nonafluorohexyltriethoxysilane Examples include silane, 1H,1H,2H,2H-perfluoro-n-octyltrimethoxysilane, 1H,2H,2H-perfluoro-n-octyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, and compounds obtained by complete or partial condensation thereof, and from the viewpoint of stability over time, polysiloxane resins containing at least one of the structures represented by the following general formulas (3) and (4) are preferred:

[0032]

[0033] R in the above general formulas (3) and (4)４ is a fluorine atom or an organic group having 1 to 20 carbon atoms and containing one or more fluorine atoms, and in the above general formula (4), R ５ and R ６ each independently represents a methyl group or a phenyl group. The wavy line in the formula indicates the bonding site.

[0034] The R ４ is a fluorine atom or an organic group having 1 to 20 carbon atoms and containing one or more fluorine atoms, and specific examples thereof include a fluoro group, a trifluoroethyl group, a trifluoropropyl group, a pentafluorophenyl group, a 1H,1H,2H,2H-nonafluorohexyl group, a 1H,1H,2H,2H-perfluoro-n-octyl group, and a 1H,1H,2H,2H-perfluorodecyl group. The organic group may have an oxygen atom or an amide bond between carbon atoms, and may further have a hydroxy group, a halogen atom, a vinyl group, an epoxy group, a glycidoxypropyl group, a styryl group, a (meth)acryloyloxypropyl group, or the like as a substituent other than a fluorine atom.

[0035] The R ４ From the viewpoint of compatibility, the number of carbon atoms in the organic group of R is 1 to 20, preferably 1 to 12, more preferably 1 to 8, even more preferably 1 to 6, and particularly preferably 1 to 3. ４ The number of fluorine atoms in the compound is 1 or more, and preferably 1 to 25 from the viewpoint of reducing the refractive index when the compound is cured.

[0036] The polysiloxane resin of this embodiment particularly preferably contains a structure represented by the following general formula (5) in addition to the structures represented by the above general formulas (3) and (4). When the polysiloxane resin of this embodiment contains the structures represented by general formulas (3) to (5), a polysiloxane resin with a desired molecular weight can be obtained.

[0037]

[0038] In the above general formula (5), R ７ and R ８ each independently represents a methyl group or a phenyl group.

[0039] In the polysiloxane resin, the molar ratio of the structures represented by the general formulas (3) and (4) to the structure represented by the general formula (5) is preferably within the range of 1:1 to 1:1.4. When the molar ratio is within the above range, the amount of hydroxyl groups and alkoxy groups in the polysiloxane resin can be suppressed, moisture absorption can be reduced, and absorption in the near-infrared region can be reduced. Furthermore, reducing unreacted hydroxyl groups in the polysiloxane resin improves stability over time and improves handleability when preparing a curable resin composition. The molar ratio of the structures represented by the general formulas (3) and (4) to the structure represented by the general formula (5) is １ H-NMR, １３ C-NMR, ２９ It can be measured by Si-NMR.

[0040] The weight-average molecular weight of the polysiloxane resin is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, even more preferably 1,500 to 10,000, and particularly preferably 2,000 to 5,000. When the weight-average molecular weight of the polysiloxane resin is 1,000 or more, the curable resin composition of this embodiment becomes tough when cured. When the weight-average molecular weight is 100,000 or less, compatibility with the (meth)acrylic acid derivative described below is improved, and the handleability of the curable resin composition is improved. The weight-average molecular weight is a polystyrene-equivalent measurement value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0041] [(A) Method for Producing Polysiloxane Resin] The method for producing the polysiloxane resin in this embodiment is not particularly limited, and any known and commonly used condensation reaction can be used. Methods for producing polysiloxane resins containing the structural formulae represented by the above general formulas (3) to (5) are shown below, but the method is not limited thereto.

[0042] The condensation reaction of the compound containing the structure represented by the general formula (3), the compound containing the structure represented by the general formula (4), and the compound containing the structure represented by the general formula (5) is carried out in the presence of an acid or basic catalyst.

[0043] Examples of the acidic catalyst include boric acid, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, triisopropoxyboron, tri-n-butoxyboron, triisobutoxyboron, tri-sec-butoxyboron, tri-tert-butoxyboron, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, Examples of the acid include tetraisopropoxytitanium (titanium tetraisopropoxide), tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra-sec-butoxytitanium, tetra-tert-butoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetraisobutoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, maleic acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0044] Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, N-ethyldiisopropylamine, dimethylaminoethanol, triethanolamine, and 2-amino-2-methyl-1-propanol.

[0045] Among these catalysts, it is preferable to use one or more of lithium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, and triethylamine from the viewpoint of reactivity.

[0046] The amount of the catalyst used is preferably 0.001 to 10% by mass, and particularly preferably 0.01 to 1% by mass, based on the total content of the compound containing the structure represented by general formula (3), the compound containing the structure represented by general formula (4), and the compound containing the structure represented by general formula (5). When the amount of the catalyst used is within the above range, the condensation reaction proceeds sufficiently, which is preferable.

[0047] In addition, during the condensation reaction of a compound containing a structure represented by general formula (3), a compound containing a structure represented by general formula (4), and a compound containing a structure represented by general formula (5), a fluorine-free siloxane monomer which may have one or more reactive groups selected from the group consisting of a (meth)acryloyl group and a styryl group may also be added in addition to the above compounds. Specific examples of such siloxane monomers include 3-(methacryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, and p-styryltrimethoxysilane.

[0048] The condensation reaction may be carried out in the absence or presence of a solvent, but is preferably carried out in the presence of a solvent in order to homogenize the reaction system. The reaction solvent may be any solvent that does not react with the raw materials, and examples thereof include ketones such as acetone and methyl ethyl ketone (MEK); aromatic hydrocarbons such as benzene, toluene, and xylene; glycols such as ethylene glycol, propylene glycol, and hexylene glycol; glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, and diethyl carbitol; and amides such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylformamide (DMF). These solvents may be used alone or in combination of two or more. Among these, toluene is preferred.

[0049] Since the condensation reaction is a dealcoholization condensation reaction, it is preferably carried out in the absence of water, and more preferably in an inert gas atmosphere such as nitrogen gas.

[0050] The reaction temperature may be adjusted appropriately to obtain a desired molecular weight distribution, and is usually 30 to 100° C. Similarly, the reaction time may be adjusted appropriately, but is usually 1 to 40 hours.

[0051] After the condensation reaction is complete, the resulting polysiloxane resin is filtered through a membrane filter, and the reaction solvent and by-product alcohol are removed under reduced pressure. It is also preferable to carry out a purification treatment as necessary.

[0052] <(B) (Meth)acrylic Acid Derivative> The curable resin composition according to this embodiment contains, as the (meth)acrylic acid derivative, a (meth)acrylic acid derivative (B-1) having a structure represented by the above general formula (1) but not containing a fluorine atom, and / or a (meth)acrylic acid derivative (B-2) having a structure represented by the above general formula (2). In this specification, (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0053] The inclusion of the specific (meth)acrylic acid derivative in the curable resin composition according to the present embodiment serves to dilute the highly viscous polysiloxane resin during preparation of the curable resin composition, thereby improving the handleability of the curable resin composition. In addition, the inclusion of the specific (meth)acrylic acid derivative improves heat resistance.

[0054] In order to ensure that the curable resin composition exhibits sufficient curability and heat resistance, the mass ratio of the polysiloxane resin to the (meth)acrylic acid derivative is preferably in the range of 99:1 to 10:90, more preferably in the range of 90:10 to 10:90, and particularly preferably in the range of 80:20 to 20:80.

[0055] In this embodiment, the (meth)acrylic acid derivative may contain at least one of the fluorine-free (meth)acrylic acid derivative (B-1) and the fluorine-containing (meth)acrylic acid derivative (B-2), but from the viewpoint of achieving both a low refractive index and heat resistance, it is preferable to contain both. Note that when only one of the fluorine-free (meth)acrylic acid derivative (B-1) and the fluorine-containing (meth)acrylic acid derivative (B-2) is contained, it is preferable to contain the fluorine-containing (meth)acrylic acid derivative (B-2) from the viewpoint of reducing the refractive index when formed into a cured product.

[0056] The (meth)acrylic acid derivative (B-1) containing no fluorine atoms and the (meth)acrylic acid derivative (B-2) containing a fluorine atom will be described in detail below.

[0057] <(B-1) Fluorine Atom-Free (Meth)acrylic Acid Derivative> In the present embodiment, the fluorine atom-free (meth)acrylic acid derivative (B-1) is characterized by having a structure represented by the following general formula (1):

[0058]

[0059] In the above general formula (1), R １ａ is a hydrogen atom or a methyl group, and Y １ is a single bond, a methylene group, or an oxyethylene group; Z １ is any one of the following general formulas (1-1) to (1-6), and n represents 1 or 2. When n is 2, a plurality of R １ａ and Y １ may be the same or different.

[0060]

[0061] In the above general formulas (1-1) and (1-4), R ２ａ is a single bond, an oxygen atom, or a methylene group, and in the general formula (1-2), R ３ａ represents a hydrogen atom or a methyl group. The wavy line in the formula represents Y in the general formula (1). １ This means that it is the binding site for

[0062] In the present embodiment, by including a fluorine atom-free (meth)acrylic acid derivative having a structure represented by the general formula (1), the aliphatic C—H bond concentration can be reduced, and absorption in the near-infrared region can be suppressed. In addition, the viscosity of the (meth)acrylic acid derivative is reduced, and when the (meth)acrylic acid derivative is formed into a curable resin composition, solidification of the curable resin composition can be suppressed.

[0063] The R １ａ may be a hydrogen atom or a methyl group, but is preferably a hydrogen atom from the viewpoint of reducing light absorption loss.

[0064] The Y １ may be a single bond, a methylene group, or an oxyethylene group, but is preferably a single bond or a methylene group from the viewpoint of reducing light absorption loss.

[0065] The R １ａ and the above Y １ may be any combination and is not particularly limited, but from the viewpoint of reducing light absorption loss, R １ａ is a hydrogen atom, Y １ is preferably a single bond or a methylene group.

[0066] In the general formula (1), Z １ is not particularly limited as long as it is any one of the above general formulas (1-1) to (1-6).

[0067] Said Z １ When the formula (1-1) or (1-4) is used, the resulting curable resin composition has particularly excellent UV curability, which is preferable.

[0068] Said Z １ However, when the compound is represented by the general formula (1-2) or (1-5), it is preferable because it has particularly excellent compatibility with polysiloxane resins.

[0069] Said Z １ When the formula (1-3) or (1-6) is used, the resulting curable resin composition is particularly excellent in heat resistance, which is preferable.

[0070] In the general formula (1), Z １is the above general formula (1-1) or (1-4), R ２ａ may be a single bond, an oxygen atom, or a methylene group, but is preferably a single bond or an oxygen atom from the viewpoint of reducing light absorption loss.

[0071] In the general formula (1), Z １ is the above general formula (1-2), R ３ａ may be a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of reducing light absorption loss.

[0072] <(B-2) Fluorine Atom-Containing (Meth)acrylic Acid Derivative> In the present embodiment, the fluorine atom-containing (meth)acrylic acid derivative (B-2) is characterized by having a structure represented by the following general formula (2).

[0073]

[0074] In the above general formula (2), R １ｂ is a hydrogen atom or a methyl group, and Y ２ is a single bond, an alkylene group having 1 to 9 carbon atoms, or an alkylene group having 1 to 9 carbon atoms and containing a fluorine atom; Z ２ represents a single bond, a hydrogen atom, a fluorine atom, or any one of the following general formulae (2-1) to (2-8), and n represents 1 or 2. In the above general formula (2), Y ２ is a single bond or an alkylene group having 1 to 9 carbon atoms, Z ２ is a fluorine atom or any one of the following general formulae (2-1) to (2-8), and Y ２ is an alkylene group having 1 to 9 carbon atoms containing a fluorine atom, Z ２ is a single bond, a hydrogen atom, a fluorine atom, or any one of the following general formulae (2-1) to (2-8). When n is 2, a plurality of R １ｂ and Y ２ may be the same or different.

[0075]

[0076] In the above general formulas (2-1) and (2-5), R ２ｂ is a single bond, an oxygen atom, or a methylene group, and in the general formula (2-2), R３ｂ is a hydrogen atom or a methyl group. At least one of the hydrogen atoms constituting the aromatic ring in the general formulae (2-1) to (2-8) is a fluorine atom or CF ３ That is, some or all of the hydrogen atoms constituting the aromatic rings in the above general formulae (2-1) to (2-8) are substituted with fluorine atoms or CF ３ The wavy line in the formula represents the Y group in the general formula (2). ２ This means that it is the binding site for

[0077] In this embodiment, since the (meth)acrylic acid derivative contains the structure represented by the general formula (2), the aliphatic C—H bond concentration can be reduced, absorption in the near-infrared region can be suppressed, and the viscosity of the (meth)acrylic acid derivative can be reduced, which can suppress solidification of the curable resin composition when it is made into a curable resin composition.In addition, the refractive index can be reduced when it is made into a cured product.

[0078] The R １ｂ may be a hydrogen atom or a methyl group, but is preferably a hydrogen atom from the viewpoint of reducing light absorption loss.

[0079] The Y ２ may be a single bond, an alkylene group having 1 to 9 carbon atoms, or an alkylene group having 1 to 9 carbon atoms and containing a fluorine atom, but is preferably a single bond or a methylene group from the viewpoint of light absorption loss. ２ is an alkylene group having 1 to 9 carbon atoms or an alkylene group having 1 to 9 carbon atoms containing a fluorine atom, the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0080] The R １ｂ and the above Y ２ Any combination may be used and is not particularly limited. However, from the viewpoint of reducing the light absorption loss, R １ｂ is a hydrogen atom, Y ２ is preferably a single bond or a methylene group.

[0081] In the general formula (2), Z ２is not particularly limited as long as it is a single bond, a hydrogen atom, a fluorine atom, or any one of the above general formulae (2-1) to (2-8). In addition, some or all of the hydrogen atoms constituting the aromatic ring in the above general formulae (2-1) to (2-8) may be replaced with fluorine atoms or CF ３ is substituted with a group.

[0082] Said Z ２ When the formula (2-1) or (2-5) is used, the resulting curable resin composition has particularly excellent UV curability, which is preferable.

[0083] Said Z ２ However, when the compound is represented by the general formula (2-2) or (2-6), it is preferable because it has particularly excellent compatibility with polysiloxane resins.

[0084] Said Z ２ When the formula (2-3) or (2-7) is used, the resulting curable resin composition is particularly excellent in heat resistance, which is preferable.

[0085] Said Z ２ When the compound represented by formula (2-4) or (2-8) is used, the resulting curable resin composition is particularly excellent in terms of light absorption loss, which is preferable.

[0086] In the general formula (2), Z ２ is the above general formula (2-1) or (2-5), R ２ｂ may be a single bond, an oxygen atom, or a methylene group, and is particularly preferably a single bond or an oxygen atom from the viewpoint of reducing light absorption loss.

[0087] In the general formula (2), Z ２ is the above general formula (2-2), R in the above general formula (2-2) ３ｂ may be a hydrogen atom or a methyl group, and is particularly preferably a hydrogen atom from the viewpoint of reducing light absorption loss.

[0088] [(B) Method for Producing (Meth)acrylic Acid Derivative] The method for producing the (meth)acrylic acid derivative in this embodiment is not particularly limited, and the derivative can be produced by a known, commonly used method.

[0089] For example, a dehydration condensation reaction between (meth)acrylic acid and a corresponding hydroxy group-containing compound may be carried out, or a dehydrohalogenation reaction between a (meth)acrylic acid halide and a corresponding hydroxy group-containing compound may be carried out in the presence of a basic substance. When a (meth)acrylic acid derivative containing a fluorine atom is produced, a hydroxy group-containing compound containing a fluorine atom may be used as the corresponding hydroxy group-containing compound.

[0090] In the case of a dehydration condensation reaction, the product can be obtained by a known method in the presence of an esterification catalyst such as p-toluenesulfonic acid or sulfuric acid and a polymerization inhibitor such as hydroquinone or phenothiazine, preferably in the presence of a solvent (e.g., toluene, benzene, cyclohexane, n-hexane, n-heptane, etc.), preferably at a temperature of 70 to 150°C. The proportion of (meth)acrylic acid used is preferably 1 to 5 mol, more preferably 1.05 to 2 mol, per mol of the hydroxy group-containing compound. The esterification catalyst is present at a concentration of preferably 0.1 to 15 mol%, more preferably 1 to 6 mol%, relative to the (meth)acrylic acid used.

[0091] In addition, in a dehydrohalogenation reaction in the presence of a basic substance, for example, (meth)acrylic acid chloride can be obtained by reacting it with a corresponding hydroxy group-containing compound. In this case, it is preferable to add a basic substance such as triethylamine, pyridine, potassium hydroxide, or sodium hydroxide. It is also preferable to add a phase transfer catalyst such as benzyltributylammonium chloride, tetrabutylammonium bromide, or benzyltriethylammonium chloride. A (meth)acrylic acid derivative can be obtained by reacting (meth)acrylic acid chloride with a corresponding hydroxy group-containing compound in the presence of a solvent (e.g., toluene, benzene, cyclohexane, n-hexane, n-heptane, acetone, tetrahydrofuran, dichlorobenzene, cyclopentyl methyl ether, etc.) or water, preferably at a temperature of −10 to 100° C.

[0092] <(C) Radical Polymerization Initiator> In the present embodiment, the radical polymerization initiator is not particularly limited as long as it initiates radical polymerization by heating or irradiation with actinic rays such as ultraviolet rays or visible light, and examples thereof include a thermal radical polymerization initiator and a photoradical polymerization initiator.

[0093] Examples of the photoradical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.

[0094] Commercially available products of these radical polymerization initiators include, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", "Irgacure-651", "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure-1800", "Irgacure-1850", "Irgacure-2959", "Irgacure-4043", and "Irgacure-1173" (Chi). Examples of suitable anti-aging agents include "Bas Specialty Chemicals," "Lucirin TPO" (manufactured by BASF), "Kayacure DETX," "Kayacure MBP," "Kayacure DMBI," "Kayacure EPA," and "Kayacure OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure 10," and "Vicure 55" (manufactured by Stauffer Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" (manufactured by Sandoz), "Deep" (manufactured by Upjohn), "Quantacure PDO," "Quantacure ITX," and "Quantacure EPD" (manufactured by Ward-Blenkinsop).

[0095] In order to achieve sufficient curability of the curable resin composition, the radical polymerization initiator is preferably in the range of 0.05 to 20 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, relative to 100 parts by mass of the curable resin composition.

[0096] The content of fluorine atoms in the curable resin composition of this embodiment is preferably 1 to 30% by mass. When the content of fluorine atoms in the curable resin composition is 1% by mass or more, the refractive index of the cured product can be reduced. Furthermore, when the content of fluorine atoms in the curable resin composition is 30% by mass or less, the cured product can adhere to a substrate. The content of fluorine atoms in the curable resin composition of this embodiment is more preferably 3 to 25% by mass, even more preferably 5 to 25% by mass, and particularly preferably 7 to 25% by mass. The content of fluorine atoms in the curable resin composition can be measured by combustion ion chromatography analysis.

[0097] <Other Components> Furthermore, if necessary, so-called additives such as a photosensitizer, an antioxidant, a surfactant, a leveling agent, a light stabilizer, and a filler may be added to the curable resin composition of the present embodiment in proportions that do not adversely affect the effects of the present invention. From the viewpoint of achieving excellent effects of the present invention, the total content of the additives is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, relative to 100 parts by mass of the curable resin composition.

[0098] (Photosensitizer) When the curable resin composition of this embodiment is cured by photopolymerization, various photosensitizers may be added in addition to the radical polymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds, and these may be used alone or in combination of two or more. When these photosensitizers are added, the amount added is preferably in the range of 0.01 to 10 parts by mass per 100 parts by mass of the curable resin composition.

[0099] (Antioxidant) An antioxidant may be added to the curable resin composition of this embodiment for the purpose of improving heat resistance. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds. When these antioxidants are added, the amount added is preferably in the range of 0.01 to 1 part by mass per 100 parts by mass of the curable resin composition.

[0100] (Surfactant) A surfactant may be added to the curable resin composition of this embodiment for the purpose of improving coatability. Examples of the surfactant include fluorine-based surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide, and fluorine-containing organosiloxane compounds. When these surfactants are added, the amount added is preferably in the range of 0.01 to 1 part by mass per 100 parts by mass of the curable resin composition.

[0101] (Light Stabilizer) As the light stabilizer, commercially available ones may be used, and examples thereof include TINUVIN (registered trademark) 123, 144, 152, 292, and 770 [all manufactured by BASF Japan Ltd.], and ADK STAB (registered trademark) LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, and LA-87 [all manufactured by ADEKA Corporation].

[0102] [Preparation of Curable Resin Composition] The method for preparing the curable resin composition of this embodiment is not particularly limited as long as the components are sufficiently mixed, but stirring and mixing using a stirring blade is generally preferred. The stirring time and stirring speed can be determined appropriately depending on the amounts of the components. From the viewpoint of ensuring sufficient mixing, the stirring time should be 1 to 24 hours and the stirring speed should be 10 to 1,000 rpm.

[0103] From the viewpoint of improving the coating property and the transparency, it is preferable to remove foreign matter from the curable resin composition using a filter. It is also preferable to remove bubbles from the curable resin composition using a defoaming device such as a vacuum pump.

[0104] The curable resin composition preferably has a viscosity that is easy to handle, for example, in the range of 500 to 100,000 mPa·s at 25° C. Furthermore, as described below, the composition may be further diluted with an organic solvent to adjust the viscosity to a desired level.

[0105] [Curable Resin Varnish] The curable resin composition of this embodiment may be diluted with an organic solvent to form a curable resin varnish for the purpose of improving coatability. The organic solvent is not particularly limited as long as it can dissolve the curable resin composition, and examples thereof include aromatic hydrocarbons, ethers, alcohols, ketones, esters, and amides. Specific examples include toluene, xylene, diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, methanol, ethanol, ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

[0106] [Cured Product] The cured product of this embodiment is obtained by curing the curable resin composition of this embodiment. The cured product of this embodiment can be obtained by uniformly mixing the components, such as the radical polymerization agent, according to the purpose, and can be formed by a method similar to a conventionally known method.

[0107] The refractive index of the cured product of this embodiment is preferably 1.56 or less, more preferably 1.52 or less, and even more preferably 1.48 or less. If the refractive index of the cured product of this embodiment is 1.56 or less, the difference in refractive index from silicon dioxide can be reduced, and therefore the cured product of this embodiment can be suitably used for optical applications such as optical communication applications. The lower limit of the refractive index is not particularly limited, but may be, for example, 1.36 or 1.46. In this specification, the "refractive index" refers to the refractive index at 25°C and the sodium D line (589 nm), and can be measured using a refractometer (for example, an Abbe refractometer manufactured by Atago Co., Ltd.).

[0108] The cured product of this embodiment preferably has an optical absorption loss at 850 nm of 0.2 dB / cm or less, more preferably 0.1 dB / cm or less. The optical absorption loss at 1310 nm is preferably 0.4 dB / cm or less, more preferably 0.2 dB / cm or less. The optical absorption loss at 1550 nm is preferably 0.6 dB / cm or less, more preferably 0.4 dB / cm or less. When the optical absorption loss at each wavelength of the cured product of this embodiment is within the above range, it is preferable that the absorption is small in the near-infrared region used in optical communication. The optical absorption loss can be measured by the following procedure. The absorbance of the test piece in the wavelength region of 400 to 2000 nm is measured using a UV-Vis-Near-Infrared Spectrophotometer (e.g., V-670, manufactured by JASCO Corporation). The test piece is prepared by the method described in the Examples below. Since the decrease in light transmittance at 800 nm corresponds to the reflected light intensity, the baseline is corrected so that the absorbance at 800 nm is zero, and the absorbance without the influence of reflection is calculated. The light absorption loss at each wavelength is measured by calculating the light absorption loss at 850 nm, 1310 nm, and 1550 nm using the following formula: Light absorption loss (dB / cm) = absorbance × 2 × 10

[0109] The cured product of this embodiment preferably has a 5% weight loss temperature (Td5) of 300°C or higher, and more preferably 350°C or higher. If the Td5 of the cured product of this embodiment is 300°C or higher, the product has excellent heat resistance and can withstand the solder reflow process. There is no particular upper limit for Td5. The 5% weight loss temperature (Td5) can be determined by measuring using a TG-DTA device (for example, TG-8120 manufactured by Rigaku Corporation) under a nitrogen flow of 20 mL / min at a temperature increase rate of 20°C / min.

[0110] [Uses] A cured product obtained by curing the curable resin composition of the present embodiment has excellent heat resistance, low optical absorption loss, and a low refractive index, and therefore can be suitably used for components used in opto-electric hybrid substrates, optical waveguides, right-angle optical path converters, optical pins, microlenses, spot size converters, optical shuffling sheets, optical converters, optical adhesives, transparent sealants, etc. Among these, it can be particularly suitably used for optical waveguides.

[0111] (Optical Waveguide) The optical waveguide of this embodiment includes the cured product of this embodiment. The optical waveguide of this embodiment may include a substrate, a cover, a mask, etc. in addition to the cured product of this embodiment.

[0112] The optical waveguide of this embodiment can be formed using the curable resin composition of this embodiment. When forming an optical waveguide using the curable resin composition of this embodiment, a known, commonly used method can be used. Typically, the optical waveguide can be formed by forming a curable resin layer on a substrate, followed by exposure and development treatments.

[0113] The substrate is not particularly limited, and examples thereof include a silicon wafer, a glass wafer, a quartz wafer, a plastic circuit board, and a ceramic circuit board.

[0114] The curable resin layer can be formed by coating the substrate with a method such as spin coating, dip coating, spray coating, bar coating, roll coating, curtain coating, gravure coating, screen coating, or inkjet coating. The amount of coating may be appropriately selected depending on the purpose. When the curable resin varnish is used, the curable resin layer may be dried after formation, if necessary.

[0115] When the curable resin layer is cured by exposure, the exposure dose is 0.01 to 10 J / cm ２ When the exposure dose is within the above range, curing proceeds sufficiently, and a fine pattern can be formed. In this case, exposure is preferably performed with light having a wavelength of 240 to 500 nm. Examples of the light having a wavelength of 240 to 500 nm include light of various wavelengths generated by a radiation generator, such as ultraviolet rays such as g-rays and i-rays, and far ultraviolet rays (248 nm).

[0116] After the exposure treatment, the film is developed using a developer, which may be an organic solvent-based developer or an alkaline developer, or a combination of these.

[0117] Examples of the organic solvent-based developer include isopropyl alcohol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

[0118] The alkaline developer may contain, as a base, for example, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal pyrophosphate, a sodium salt, an ammonium salt, or an organic salt.

[0119] The following examples of the present invention will be described in more detail, but the present invention is not limited to these examples.

[0120] [Evaluation Method] <Evaluation of Light Absorption Loss> A curable resin composition was poured into a fluororubber O-ring placed on a glass plate, and the composition was sandwiched between two glass plates from above, taking care not to trap air bubbles. ２ The cured product was irradiated with light of 1000 nm to obtain a cured product. The cured product was peeled off from the glass plate and O-ring to obtain a test piece with a diameter of 20 mm and a thickness of 5 mm. The absorbance of the test piece in the wavelength range of 400 to 2000 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (V-670, manufactured by JASCO Corporation). Since the decrease in light transmittance at 800 nm corresponds to the reflected light intensity, the baseline was corrected so that the absorbance at 800 nm was zero, and the absorbance without the influence of reflection was calculated. The light absorption loss at 850 nm, 1310 nm, and 1550 nm was calculated using the following formula: Light absorption loss (dB / cm) = absorbance × 2 × 10

[0121] <Evaluation of Refractive Index> The refractive index of the test piece prepared in the same manner as in the above <Evaluation of Light Absorption Loss> was measured at the sodium D line (589 nm) using an Abbe refractometer manufactured by Atago Co., Ltd.

[0122] <Evaluation of Heat Resistance> Using a TG-DTA device (TG-8120, manufactured by Rigaku Corporation), measurements were carried out under a nitrogen flow of 20 mL / min at a temperature increase rate of 20° C. / min to measure the 5% weight loss temperature (Td5).

[0123] <Evaluation of Weight-Average Molecular Weight> The weight-average molecular weight was measured using the following measuring device and under the following measuring conditions. Measurement apparatus: "HLC-8320 GPC" manufactured by Tosoh Corporation Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Developing solvent tetrahydrofuran Flow rate 1.0 mL / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual for the "GPC workstation EcoSEC-WorkStation". (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" Tosoh Corporation "F-1" Tosoh Corporation "F-2" Tosoh Corporation "F-4" Tosoh Corporation "F-10" Tosoh Corporation "F-20" Tosoh Corporation "F-40" Tosoh Corporation "F-80" Tosoh Corporation "F-128"

[0124] (Production Example 1) A 2 L flask equipped with a thermometer, condenser, and stirrer was charged with 216.3 g (1 mol) of diphenylsilanediol, 124.2 g (0.5 mol) of 3-(methacryloyloxy)propyltrimethoxysilane, 109.1 g (0.5 mol) of 3,3,3-trifluoropropyltrimethoxysilane, and 283.0 g of toluene, and the mixture was heated to 50°C with stirring. Then, 0.38 g of barium hydroxide monohydrate was added, and the mixture was allowed to react at 50°C for 20 hours. After completion of the reaction, the resulting reaction mixture was cooled to room temperature and filtered using a membrane filter with a pore size of 0.2 μm. Toluene and the by-product methanol were removed under reduced pressure using a rotary evaporator. A polysiloxane (A1) having a weight average molecular weight of 2900 and containing methacryloyl groups was obtained.

[0125] (Production Example 2) Synthesis was carried out in the same manner as in Production Example 1, except that the amount of 3-(methacryloyloxy)propyltrimethoxysilane in Production Example 1 was changed from 124.2 g (0.5 mol) to 235.9 g (0.95 mol) and the amount of 3,3,3-trifluoropropyltrimethoxysilane was changed from 109.1 g (0.5 mol) to 10.9 g (0.05 mol), to obtain polysiloxane (A2) having methacryloyl groups and a weight average molecular weight of 2700.

[0126] Production Example 3 Synthesis was carried out in the same manner as in Production Example 1, except that the amount of diphenylsilanediol in Production Example 1 was changed from 216.3 g (1 mol) to 92.2 g (0.5 mol) of dimethylhydroxysilane, 3-(methacryloyloxy)propyltrimethoxysilane from 124.2 g (0.5 mol) to 12.4 g (0.05 mol), and 3,3,3-trifluoropropyltrimethoxysilane from 109.1 g (0.5 mol) to 207.3 g (0.95 mol), to obtain polysiloxane (A3) having methacryloyl groups and a weight average molecular weight of 3,000.

[0127] (Production Example 4) Synthesis was carried out in the same manner as in Production Example 1, except that 124.2 g (0.5 mol) of 3-(methacryloyloxy)propyltrimethoxysilane in Production Example 1 was changed to 117.2 g (0.5 mol) of 3-(acryloyloxy)propyltrimethoxysilane, to obtain polysiloxane (A4) having acryloyl groups and a weight average molecular weight of 2,800.

[0128] (Production Example 5) Synthesis was carried out in the same manner as in Production Example 1, except that 124.2 g (0.5 mol) of 3-(methacryloyloxy)propyltrimethoxysilane in Production Example 1 was changed to 112.2 g (0.5 mol) of p-styryltrimethoxysilane, to obtain polysiloxane (A5) having a styryl group and a weight average molecular weight of 2,800.

[0129] (Production Example 6) Synthesis was carried out in the same manner as in Production Example 1, except that the amount of diphenylsilanediol used in Production Example 1 was changed from 216.3 g (1 mol) to 194.7 g (0.9 mol), to obtain polysiloxane (A6) having methacryloyl groups and a weight average molecular weight of 2,600.

[0130] (Production Example 7) Synthesis was carried out in the same manner as in Production Example 1, except that the amount of diphenylsilanediol used in Production Example 1 was changed from 216.3 g (1 mol) to 324.5 g (1.5 mol), to obtain polysiloxane (A7) having methacryloyl groups and a weight average molecular weight of 3,600.

[0131] (Production Example 8) 24.06 g of 4-phenoxyphenol, 96.23 g of dichloromethane, and 15.69 g of triethylamine were charged into a 200 mL flask equipped with a thermometer, a condenser, and a stirrer, and the mixture was cooled to 0°C in an ice bath with stirring. Thereafter, 14.03 g of acrylic acid chloride was added dropwise over 5 hours. The temperature was then returned to room temperature, 25°C, and the reaction was continued for another 5 hours. Thereafter, stirring was stopped, and the reaction solution was washed 10 times with pure water. Thereafter, dichloromethane was distilled from the reaction solution under reduced pressure using an evaporator, and an acrylic acid derivative (B-1-1) having the following structural formula was obtained.

[0132]

[0133] (Production Example 9) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 23.80 g of 4-benzylphenol, to obtain an acrylic acid derivative (B-1-2) of the following structural formula.

[0134]

[0135] (Production Example 10) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 21.99 g of orthophenylphenol, to obtain an acrylic acid derivative (B-1-3) of the following structural formula.

[0136]

[0137] (Production Example 11) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 23.80 g of [1,1'-biphenyl]-3-methanol, to obtain an acrylic acid derivative (B-1-4) of the following structural formula.

[0138]

[0139] (Production Example 12) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 25.87 g of 3-phenoxybenzyl alcohol, to obtain an acrylic acid derivative (B-1-5) of the following structural formula.

[0140]

[0141] (Production Example 13) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 27.68 g of orthophenylphenoxyethanol, to obtain an acrylic acid derivative (B-1-6) of the following structural formula.

[0142]

[0143] (Production Example 14) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 23.81 g of diphenylmethanol, to obtain an acrylic acid derivative (B-1-7) of the following structural formula.

[0144]

[0145] (Production Example 15) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 25.62 g of 1,1-diphenylethanol, to obtain an acrylic acid derivative (B-1-8) of the following structural formula.

[0146]

[0147] (Production Example 16) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 20.44 g of 1-naphthalenemethanol, to obtain an acrylic acid derivative (B-1-9) of the following structural formula.

[0148]

[0149] (Production Example 17) The synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 12.03 g of 2,2'-biphenol, to obtain an acrylic acid derivative (B-1-10) of the following structural formula.

[0150]

[0151] (Production Example 18) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 13.84 g of 1,1-diphenyl-1,2-ethanediol, to obtain an acrylic acid derivative (B-1-11) of the following structural formula.

[0152]

[0153] (Production Example 19) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 12.16 g of 1,5-naphthalenedimethanol, to obtain an acrylic acid derivative (B-1-12) of the following structural formula.

[0154]

[0155] (Production Example 20) Synthesis was carried out in the same manner as in Production Example 8, except that the amount of acrylic acid chloride used in Production Example 8 was changed to 16.20 g of methacrylic acid chloride, thereby obtaining an acrylic acid derivative (B-1-13) having the following structural formula.

[0156]

[0157] (Production Example 21) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 26.38 g of 3-fluoro-4-phenoxyphenol, to obtain an acrylic acid derivative (B-2-1) of the following structural formula.

[0158]

[0159] (Production Example 22) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 28.45 g of 2,6-difluoro-4-(phenylmethyl)phenol, to obtain an acrylic acid derivative (B-2-2) of the following structural formula.

[0160]

[0161] (Production Example 23) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 24.32 g of 3-fluoro[1,1'-biphenyl]-4-ol, to obtain an acrylic acid derivative (B-2-3) of the following structural formula.

[0162]

[0163] (Production Example 24) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 26.13 g of 2-fluoro[1,1'-biphenyl]-4-methanol, to obtain an acrylic acid derivative (B-2-4) of the following structural formula.

[0164]

[0165] (Production Example 25) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 48.60 g of 2-[(2,2',3,3',4',5,5',6,6'-nonafluoro[1,1'-biphenyl]-4-yl)oxy]ethanol, to obtain an acrylic acid derivative (B-2-5) having the following structural formula.

[0166]

[0167] (Production Example 26) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 26.13 g of 3-fluoro-α-phenylbenzenemethanol, to obtain an acrylic acid derivative (B-2-6) of the following structural formula.

[0168]

[0169] (Production Example 27) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 27.94 g of 3-fluoro-α-methyl-α-phenylbenzenemethanol, to obtain an acrylic acid derivative (B-2-7) of the following structural formula.

[0170]

[0171] (Production Example 28) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 22.77 g of 8-fluoro-2-naphthalenemethanol, to obtain an acrylic acid derivative (B-2-8) of the following structural formula.

[0172]

[0173] (Production Example 29) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 23.78 g of pentafluorophenol, to obtain an acrylic acid derivative (B-2-9) of the following structural formula.

[0174]

[0175] (Production Example 30) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 13.19 g of 5-fluoro[1,1'-biphenyl]-2,2'-diol, to obtain an acrylic acid derivative (B-2-10) of the following structural formula.

[0176]

[0177] (Production Example 31) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 16.17 g of 1,2-ethanediol,1-(3,5-difluorophenyl)-1-phenyl, to obtain an acrylic acid derivative (B-2-11) having the following structural formula.

[0178]

[0179] (Production Example 32) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 19.13 g of 1,3,4,5,7,8-hexafluoro-2,6-naphthalenedimethanol, to obtain an acrylic acid derivative (B-2-12) having the following structural formula.

[0180]

[0181] (Production Example 33) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 23.53 g of tetrafluorohydroquinone, to obtain an acrylic acid derivative (B-2-13) of the following structural formula.

[0182]

[0183] (Production Example 34) Synthesis was carried out in the same manner as in Production Example 8, except that 24.06 g of 4-phenoxyphenol in Production Example 8 was changed to 30.24 g of 2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenol, to obtain an acrylic acid derivative (B-2-14) of the following structural formula.

[0184]

[0185] (Production Example 35) Synthesis was carried out in the same manner as in Production Example 8, except that the 14.03 g of acrylic acid chloride in Production Example 8 was changed to 16.20 g of methacrylic acid chloride, and further, the 24.06 g of 4-phenoxyphenol was changed to 26.38 g of 3-fluoro-4-phenoxyphenol, to obtain a methacrylic acid derivative (B-2-15) having the following structural formula.

[0186]

[0187] Comparative Production Example 1 Synthesis was carried out in the same manner as in Production Example 1, except that 109.1 g (0.5 mol) of 3,3,3-trifluoropropyltrimethoxysilane in Production Example 1 was changed to 99.1 g (0.5 mol) of phenyltrimethoxysilane, to obtain a fluorine-atom-free polysiloxane (comparative component (A), A8) having a weight-average molecular weight of 2800 and having methacryloyl groups.

[0188] Using the polysiloxanes (A1) to (A8) as the polysiloxane resin, the acrylic acid derivatives (B-1-1) to (B-1-13) as the fluorine-free (meth)acrylic acid derivatives, the acrylic acid derivatives (B-2-1) to (B-2-15) as the fluorine-containing (meth)acrylic acid derivatives, and 2,2,2-trifluoroethyl acrylate, and 2-hydroxy-2-methyl-1-phenylpropan-1-one (HMPP) as the radical polymerization agent, curable resin compositions were prepared and evaluated according to the formulations in Tables 1 to 4 below. In Comparative Example 4, benzyl acrylate (comparative (B) component) was used instead of the (B) component ((meth)acrylic acid derivative) obtained in the above Production Example.

[0189]

[0190]

[0191]

[0192]

[0193] As can be seen from Tables 1 to 4 above, the curable resin compositions of Examples 1 to 42, when cured, had excellent heat resistance due to their high 5% weight loss temperatures, small light absorption loss, and low refractive index. On the other hand, Comparative Example 1 did not contain a (meth)acrylic acid derivative, and therefore had a low 5% weight loss temperature. Comparative Example 2 had a high refractive index due to the absence of fluorine atoms in the polysiloxane resin. Comparative Example 3 was an example in which the polysiloxane resin did not contain fluorine atoms, and therefore had a low 5% weight loss temperature. Comparative Example 4 used benzyl acrylate instead of component (B) (a (meth)acrylic acid derivative), and therefore had a large light absorption loss.

Claims

1. A curable resin composition containing the following components (A) to (C): (A) a polysiloxane resin having at least one reactive group selected from the group consisting of a (meth)acryloyl group and a styryl group, and an organic group containing a fluorine atom; (B) a (meth)acrylic acid derivative (B-1) containing no fluorine atom and having a structure represented by the following general formula (1), and / or a (meth)acrylic acid derivative (B-2) containing a fluorine atom and having a structure represented by the following general formula (2): (In the above general formula (1), R １ａ is a hydrogen atom or a methyl group, and Y １ is any one of a single bond, a methylene group, and an oxyethylene group; Z １ is any one of the following general formulas (1-1) to (1-6), and n is 1 or 2. When n is 2, multiple R １ａ and Y １ may be the same or different.) (In the above general formulas (1-1) and (1-4), R ２ａ is a single bond, an oxygen atom or a methylene group, and in the above general formula (1-2), R ３ａ represents a hydrogen atom or a methyl group.) (In the above general formula (2), R １ｂ is a hydrogen atom or a methyl group, and Y ２ is a single bond, an alkylene group having 1 to 9 carbon atoms, or an alkylene group having 1 to 9 carbon atoms and containing a fluorine atom; Z ２ represents a single bond, a hydrogen atom, a fluorine atom, or any one of the following general formulae (2-1) to (2-8), and n represents 1 or 2. In the above general formula (2), Y ２ is a single bond or an alkylene group having 1 to 9 carbon atoms, Z ２ is a fluorine atom or any one of the following general formulae (2-1) to (2-8), and Y ２ is an alkylene group having 1 to 9 carbon atoms containing a fluorine atom, Z ２ is a single bond, a hydrogen atom, a fluorine atom, or any one of the following general formulae (2-1) to (2-8). １ｂ and Y ２ may be the same or different.) (In the above general formulas (2-1) and (2-5), R ２ｂ is a single bond, an oxygen atom or a methylene group, and in the above general formula (2-2), R ３ｂ is a hydrogen atom or a methyl group. At least one of the hydrogen atoms constituting the aromatic ring in the above general formulas (2-1) to (2-8) is a fluorine atom or CF ３ (C) Radical Polymerization Initiator 2. The curable resin composition according to claim 1, wherein the mass ratio of said component (A) to said component (B) is 99:1 to 10:

90.

3. R ​​in the general formula (1) １ａ is a hydrogen atom, and Y １ The curable resin composition according to claim 1 or 2, wherein represents a single bond or a methylene group.

4. R in the general formulas (1-1) and (1-4) ２ａ and R in the general formulas (2-1) and (2-5) ２ｂ The curable resin composition according to claim 1 or 2, wherein represents a single bond or an oxygen atom.

5. R in the general formula (1-2) ３ａ and R in the general formula (2-2) ３ｂ The curable resin composition according to claim 1 or 2, wherein is a hydrogen atom.

6. The curable resin composition according to claim 1 or 2, wherein the content of fluorine atoms in the component (A) is 1 to 24 mass %.

7. The curable resin composition according to claim 1 or 2, wherein the component (A) contains at least one of the structures represented by the following general formulas (3) and (4). (In the above general formulas (3) and (4), R ４ is a fluorine atom or an organic group having 1 to 20 carbon atoms and containing one or more fluorine atoms, and in the above general formula (4), R ５ and R ６ each independently represents a methyl group or a phenyl group.) 8. The curable resin composition according to claim 7, wherein the component (A) further contains a structure represented by the following general formula (5), and the molar ratio of the structures represented by general formulas (3) and (4) to the structure represented by general formula (5) is 1:1 to 1:1.

4. (In the above general formula (5), R ７ and R ８ each independently represents a methyl group or a phenyl group.) 9. A cured product obtained by curing the curable resin composition according to claim 1 or 2.

10. An optical waveguide comprising the cured product according to claim 9.

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