Curable resin, curable resin composition and cured product

Abstract

The purpose of the present invention is to provide: a material with which it is possible to obtain a cured product having low absorption (low light absorption loss) in the near-infrared region used in optical communication, excellent heat resistance, and excellent productivity (UV curability); and an optical waveguide or optical adhesive using the material. Specifically, the present invention is characterized by preparing a curable resin composition containing, as essential components, (A) a polysiloxane resin having one or more reactive groups selected from the group consisting of a (meth) acryloyl group and a styryl group, (B) a (meth) acrylic acid derivative having a structure represented by general formula (1), and (C) a compound represented by general formula (2). (C) a radical polymerization initiator).

Description

Technical Field

[0001] The present invention relates to a polymerizable composition (hereinafter sometimes simply referred to as "resin") useful as an optical waveguide, or an optical adhesive, or a transparent sealant, or related components thereof that can be used in optical applications such as optical communication applications and optical integrated circuit applications, and a cured product manufactured from the resin. Background Art

[0002] In recent years, the requirements for higher speed and higher capacity in communication and signal transmission have been increasing. In the internal wiring of devices, the importance of signal transmission using light instead of electricity is also increasing. This short-distance optical communication technology is called optical interconnection, and as its component, the development of an optoelectronic hybrid substrate in which a part of the electrical wiring formed of copper on a printed circuit board is replaced with optical wiring formed of an optical fiber or an optical waveguide is actively underway.

[0003] As the required characteristics of the material used in an optical waveguide, there are small absorption in the near-infrared region used in optical communication and excellent productivity. Conventionally, a quartz-based material has been generally used as the material for an optical waveguide, but in recent years, an optical waveguide using a polymer material with low cost and easy processability has been actively studied.

[0004] For example, a fluorinated polyimide that can be used as an optical material for an optical waveguide has been reported (Patent Document 1). However, in the fluorinated polyimide-based material, although the CH groups in the molecule are few and the absorption in the near-infrared region is small, since sintering at a high temperature is required, there are also problems such as cracks caused by stress due to the difference in the linear expansion rate between the substrate and the film, and the need for reactive ion etching for patterning, which increases the number of processes and deteriorates the productivity.

[0005] As a material that can be patterned by photolithography and has no by-products, an organic / inorganic hybrid material having an organic reactive group and a siloxane skeleton has been reported (Patent Document 2). However, the absorption in the near-infrared region cannot be said to be sufficiently small, and further improvement is required.

[0006] Furthermore, since the polymer material for an optical waveguide is exposed to high-temperature reflow soldering during circuit formation, a material with excellent heat resistance is required. Especially recently, from the viewpoint of environmental problems, since lead-free solder with a high melting point is used, the requirement for a polymer material for an optical waveguide with even higher heat resistance has increased.

[0007] In order to improve the reliability of components, a light-receiving and light-emitting component that transmits and receives light through an optical waveguide of an optoelectronic composite substrate is sealed using a transparent optical adhesive. For example, a light-receiving and light-emitting component such as a surface-emitting laser element (VCSEL) is connected to an optical waveguide on a substrate using an optical adhesive, and then soldered using reflow soldering, thereby connecting the electrical wiring to the light-receiving and light-emitting component and fixing the component. Therefore, such an optical adhesive also requires the same performance as the material used in the optical waveguide.

[0008] In order to solve this problem, for example, a resin composition characterized by containing a liquid aliphatic epoxy compound and a specific aromatic epoxy compound (Patent Document 3), or a curable resin composition characterized by containing a (meth)acrylate having an alicyclic hydrocarbon group (Patent Document 4) has been developed. However, the absorption in the near-infrared region cannot be said to be sufficiently small, and further improvement is required.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Patent Laid-Open No. 5-01148

[0012] Patent Document 2: U.S. Patent No. 6,984,483 Specification

[0013] Patent Document 3: Japanese Patent Laid-Open No. 2020-184091

[0014] Patent Document 4: Japanese Patent Laid-Open No. 11-61081 Summary of the Invention

[0015] Problems to be Solved by the Invention

[0016] An object of the present invention is to provide a material, an optical waveguide, and an optical adhesive using the material, the material capable of obtaining a cured product having low absorption (low light absorption loss) in the near-infrared region used in optical communication, excellent heat resistance, and excellent productivity (UV curability).

[0017] Means for Solving the Problems

[0018] In order to solve the above problems, the present inventors conducted in-depth research. As a result, it was found that a curable resin composition containing a specific (meth)acrylic derivative has low light absorption loss, high heat resistance, and excellent UV curability, and thus the present invention was completed.

[0019] That is, the present invention is as follows.

[0020] (1) A curable resin composition containing the following components (A) to (C) as essential components.

[0021] (A) A polysiloxane resin having at least one reactive group selected from the group consisting of (meth)acryloyl group and styryl group;

[0022] (B) A (meth)acrylic acid derivative having a structure represented by the following general formula (1);

[0023] (C) A radical polymerization initiator.

[0024]

[0025] (In the above general formula (1), R1 is a hydrogen atom or a methyl group, Y is a single bond, a methylene group or an oxyethylene group, Z is any one of the following general formulas (1-1) to (1-8), and n represents 1 to 6. It should be noted that when n is 2 to 6, multiple R1 and Y are optionally the same or different.)

[0026]

[0027] (In the above general formulas (1-1) to (1-10), R2 is a single bond, an oxygen atom or a methylene group, R3 is a hydrogen atom or a methyl group, and R4 represents a direct bond, a single bond or a phenyl group.)

[0028] (2) The curable resin composition according to the above (1), wherein n in the above general formula (1) is 1 or 2.

[0029] (3) The curable resin composition according to the above (1) or (2), wherein the mass ratio of the above component (A) to the above component (B) is 99:1 to 10:90.

[0030] (4) The curable resin composition according to any one of the above (1) to (3), wherein R1 in the above general formula (1) is a hydrogen atom, and Y is a single bond or a methylene group.

[0031] (5) The curable resin composition according to any one of the above (1) to (4), wherein R2 in the above general formulas (1-1) and (1-4) is a single bond or an oxygen atom.

[0032] (6) The curable resin composition according to any one of the above (1) to (5), wherein R3 in the above general formula (1-2) is a hydrogen atom.

[0033] (7) The curable resin composition according to any one of the above (1) to (6), wherein the above component (A) contains the structural formulas represented by the following general formulas (2) and (3).

[0034]

[0035] (In the above general formulas (2) and (3), R4 represents an organic group having 1 to 12 carbon atoms, and R5 and R6 each independently represent a methyl group or a phenyl group.)

[0036] (8) The curable resin composition according to (7) above, wherein, in the component (A), the molar ratio of the above general formula (2) to the above general formula (3) is 1:0.9 to 1:1.5.)

[0037] Effects of the Invention

[0038] According to the present invention, a curable resin composition can be provided, which has low light absorption loss, high heat resistance, excellent UV curability, and excellent workability by using a polysiloxane resin having a specific reactive group, a (meth)acrylic acid derivative having a specific structure, and a radical polymerization initiator as essential components.) Detailed Description of the Invention

[0039] Hereinafter, embodiments of the present invention will be described in detail.)

[0040] [Curable Resin Composition

[0041] The curable resin composition of the present embodiment contains (A) a polysiloxane resin, (B) a (meth)acrylic acid derivative, and (C) a radical polymerization initiator as essential components.)

[0042] <(A) Polysiloxane Resin>

[0043] The above polysiloxane resin has one or more reactive groups selected from the group consisting of (meth)acryloyl and styryl groups. Among the radically polymerizable groups, from the viewpoint of UV curability, having the above reactive groups is particularly preferred. It should be noted that in this specification, (meth)acryloyl means acryloyl or methacryloyl.)

[0044] The above polysiloxane resin only needs to have at least one or more of the above reactive groups, and can be two or more, or three or more. For example, if it is (meth)acryloyl, the UV curability is particularly excellent, and if it is styryl, the low light absorption loss is particularly excellent and is preferred. As long as the appropriate ratio is selected according to the required physical properties, it can contain only any one of the reactive groups or contain any reactive groups, and there is no particular limitation. It should be noted that from the viewpoint of UV curability, it is more preferable that one molecular chain of the polysiloxane resin has one or more of the above reactive groups, and particularly preferably has two or more.)

[0045] In the above polysiloxane resin, if the concentration of the reactive group is 500 to 10,000 mmol / kg, sufficient curability can be obtained, so it is preferred.)

[0046] The polysiloxane resin of the present embodiment is not particularly limited as long as it has a siloxane backbone. For example, organotrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styrylmethoxysilane, p-styrylethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, or 3-(meth)acryloxypropyltriethoxysilane; diorganodialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylcyclohexyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, or 3-(meth)acryloxypropylmethyldiethoxysilane; various chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3-(meth)acryloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, or diphenyldichlorosilane; tetraethoxysilane, tetramethoxysilane, diphenylsilanediol, ditolylsilanediol, bis(4-ethylphenyl)silanediol, bis(4-isopropylphenyl)silanediol, dinaphthylsilanediol, 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, etc.; those obtained by making their complete or partial condensates. From the viewpoints of curability and flexibility, a polysiloxane resin containing the structural formula represented by the following general formula (2) and the structural formula represented by the following general formula (3) is particularly preferred.

[0047]

[0048] In the above general formulas (2) and (3), R4 represents an organic group having 1 to 12 carbon atoms, and R5 and R6 each independently represent a methyl group or a phenyl group. It should be noted that the wavy line portion represents the bonding site.

[0049] Examples of the organic group having 1 to 12 carbon atoms in the aforementioned R4 include: linear alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl; alkoxy groups such as methoxy and ethoxy; cyclic alkyl groups such as cyclohexyl and norbornyl; alkenyl groups such as vinyl, 1-propenyl, allyl, butenyl, and 1,3-butadienyl; alkynyl groups such as ethynyl, propynyl, and butynyl; halogenated alkyl groups such as trifluoromethyl; alkyl groups having a saturated heterocyclic group such as 3-pyrrolidinopropyl; aryl groups such as phenyl optionally having an alkyl substituent; aralkyl groups such as phenylmethyl and phenylethyl, etc. It should be noted that oxygen atoms, amide bonds, etc. may be present between the carbon atoms of the organic group, and hydroxyl groups, halogen atoms, vinyl groups, epoxy groups, epoxypropoxypropyl groups, styryl groups, (meth)acryloyloxypropyl groups, etc. may also be present as substituents.

[0050] In the polysiloxane resin, the molar ratio of the structural formulas represented by the above general formulas (2) and (3) is preferably in the range of 1:0.9 to 1:1.5, and particularly preferably in the range of 1:1 to 1:1.4. If the molar ratio of the structural formula represented by the general formula (3) is 0.9 or more, the amount of hydroxyl groups in the polysiloxane resin can be suppressed, the moisture absorption of water can be reduced, and the absorption in the near-infrared region can be decreased. In addition, if the molar ratio of the structural formula represented by the general formula (3) is 1.5 or less, the unreacted hydroxyl groups in the polysiloxane resin are reduced, and further solidification of the polysiloxane resin is suppressed. Therefore, the operability in preparing the curable resin composition is improved, so it is preferred.

[0051] The weight-average molecular weight of the aforementioned polysiloxane resin is preferably 1,000 to 100,000, and more preferably 1,500 to 50,000. If it is 1,000 or more, the molecular weight is large and the cured product becomes tough. If it is 100,000 or less, when preparing the curable resin composition, the compatibility with the (meth)acrylic derivative described later is good and the operability is also excellent, so it is preferred. It should be noted that the aforementioned weight-average molecular weight is a polystyrene conversion measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the elution solvent.

[0052] [(A) Method for manufacturing polysiloxane resin]

[0053] The method for manufacturing the polysiloxane resin in the present embodiment is not particularly limited, and known and commonly used condensation reactions can be used. Hereinafter, a method for manufacturing a polysiloxane resin containing the structural formula represented by the above general formula (2) and the structural formula represented by the above general formula (3) is shown, but it is not limited to these.

[0054] The condensation reaction between the compound containing the structural formula represented by the above general formula (2) and the compound containing the structural formula represented by the above general formula (3) is carried out in the presence of an acidic catalyst or a basic catalyst.

[0055] Examples of the aforementioned acidic catalyst include: boric acid, trimethoxyborane, triethoxyborane, tri-n-propoxyborane, triisopropoxyborane, tri-n-butoxyborane, triisobutoxyborane, tri-sec-butoxyborane, tri-tert-butoxyborane, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium (tetraisopropyl titanate), tetra-n-butoxytitanium, tetra-isobutoxytitanium, tetra-sec-butoxytitanium, tetra-tert-butoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetra-isobutoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, maleic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.

[0056] Examples of the aforementioned 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, 2-amino-2-methyl-1-propanol, etc.

[0057] Among these catalysts, any one of magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, and triethylamine is particularly preferred.

[0058] Relative to the total mass of the compound containing the structural formula represented by the above general formula (2) and the compound containing the structural formula represented by the above general formula (3), the usage amount of the aforementioned catalyst is preferably 0.001 to 10% by mass, and particularly preferably 0.01 to 1% by mass. If it is within the aforementioned range, the condensation reaction proceeds sufficiently, so it is preferred.

[0059] The condensation reaction can be carried out without a solvent or in the presence of a solvent. In order to make the reaction system uniform, it is preferably carried out in the presence of a solvent. As the reaction solvent, as long as it does not react with the raw materials, examples include: ketones such as acetone and methyl ethyl ketone (MEK); aromatic hydrocarbons such as benzene, toluene, and xylene; diols such as ethylene glycol, propylene glycol, and hexanediol; glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, and diethyl carbitol; amides such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylformamide (DMF), etc. These solvents can be used alone or in combination of two or more. Among these, toluene is preferred.

[0060] The condensation reaction is a de-alcohol condensation reaction. Therefore, it is preferably carried out in the absence of water and preferably in an inert gas atmosphere such as nitrogen.

[0061] The reaction temperature can be appropriately adjusted as long as it results in the desired molecular weight distribution, and it is usually sufficient to be 30 to 100 °C. In addition, the reaction time can also be appropriately adjusted in the same way, and it is usually 1 to 40 hours.

[0062] After the condensation reaction is completed, the obtained polysiloxane resin is filtered using a membrane filter, and the reaction solvent and the alcohol as a by-product are removed under reduced pressure. In addition, purification treatment is preferably carried out as needed.

[0063] <(B) (Meth) acrylic acid derivative>

[0064] The aforementioned (meth) acrylic acid derivative is characterized by having a structure represented by the following general formula (1).

[0065]

[0066] In the above general formula (1), R1 is a hydrogen atom or a methyl group, Y is a single bond, a methylene group or an oxyethylene group, Z is any one of the following general formulas (1-1) to (1-6), and n represents 1 to 6. It should be noted that when n is 2 to 6, multiple R1 and Y may be the same or different.

[0067]

[0068] In the above general formulas (1-1) to (1-10), R2 is a single bond, an oxygen atom or a methylene group, R3 is a hydrogen atom or a methyl group, and R4 represents a direct bond, a single bond or a phenyl group. It should be noted that the wavy line part in the formula refers to the bonding site with Y.

[0069] In the above general formulas (1-7) to (1-10), the wavy line part is the bonding site with Y, but it is not necessary for all the wavy line parts to be bonded to Y, and it is sufficient to be bonded to at least one or more Y.

[0070] It should be noted that in the present invention, the (meth) acrylic acid derivative may include one or more kinds. As described later, due to the structure of Z, there are particularly excellent physical properties. Therefore, in order to achieve the desired physical properties, a variety of (meth) acrylic acid derivatives can be appropriately combined and used.

[0071] In the present embodiment, by using the aforementioned (meth) acrylic acid derivative as an essential component, when preparing the curable resin composition, it can play a role in diluting the highly viscous polysiloxane resin and improve the operability of the curable resin composition.

[0072] In the present embodiment, by making the (meth)acrylic acid derivative contain the structure represented by the above general formula (1), the concentration of aliphatic C-H bonds can be reduced, absorption in the near-infrared region can be suppressed, and in addition, the viscosity of the (meth)acrylic acid derivative is reduced, and solidification of the above-mentioned curable resin composition can be suppressed when the curable resin composition is prepared.

[0073] The aforementioned R1 may be a hydrogen atom or a methyl group, and from the viewpoint of reducing light absorption loss, it is particularly preferably a hydrogen atom.

[0074] The aforementioned Y may be a single bond, a methylene group or an oxyethylene group, and from the viewpoint of reducing light absorption loss, it is particularly preferably a single bond or a methylene group.

[0075] The aforementioned R1 and the aforementioned Y may be any combination and are not particularly limited. From the viewpoint of reducing light absorption loss, it is particularly preferably the case where R1 is a hydrogen atom and Y is a single bond or a methylene group.

[0076] The aforementioned n represents 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2. By being within the aforementioned range, when the resin composition is prepared, it has low light absorption loss, high heat resistance, and excellent UV curability, and thus is preferred. In particular, if n is 1 or 2, the viscosity of the (meth)acrylic acid derivative is particularly low and the operability is also excellent, and thus is preferred.

[0077] In the above general formula (1), Z is not particularly limited as long as it is any one of the above general formulas (1-1) to (1-10).

[0078] If Z is the general formula (1-1) or (1-4), the UV curability of the obtained curable resin composition is particularly excellent, and thus is preferred.

[0079] If Z is the general formula (1-2) or (1-5), the compatibility with the polysiloxane resin is particularly excellent, and thus is preferred.

[0080] If Z is the general formula (1-3) or (1-6), the heat resistance of the obtained curable resin composition is particularly excellent, and thus is preferred.

[0081] If Z is the general formula (1-7) or (1-8), the heat resistance of the obtained curable resin composition is particularly excellent, and thus is preferred.

[0082] In the above general formula (1), when Z is the above general formula (1-1) or (1-4), R2 in the formula may be a single bond, an oxygen atom or a methylene group, and from the viewpoint of reducing light absorption loss, it is particularly preferably a single bond or an oxygen atom.

[0083] In the aforementioned general formula (1), when Z is the aforementioned general formula (1-2) or (1-7), R3 in the formula may be a hydrogen atom or a methyl group, and from the viewpoint of reducing light absorption loss, a hydrogen atom is particularly preferred.

[0084] In the aforementioned general formula (1), when Z is the aforementioned general formula (1-8), R4 in the formula may be a single bond or a phenyl group, and from the viewpoint of solvent solubility, a single bond is particularly preferred.

[0085] In the aforementioned general formula (1), when Z is the aforementioned general formulas (1-1) to (1-6), the obtained (meth)acrylic acid derivative is liquid, and when compounded with a polysiloxane resin, a solvent-free system that does not require dilution with a solvent can be prepared, so it is particularly preferred.

[0086] In the aforementioned general formula (1), when Z is the aforementioned general formulas (1-7) to (1-10), the obtained (meth)acrylic acid derivative is solid, and when compounded with a polysiloxane resin, it is preferably diluted with a solvent before use. It should be noted that by combining with the (meth)acrylic acid derivative in which Z in the aforementioned general formula (1) is the aforementioned general formulas (1-1) to (1-6) and compounding with a polysiloxane resin, use as a solvent-free system can also be achieved.

[0087] As described above, when using a plurality of (meth)acrylic acid derivatives in combination, an appropriate compounding ratio can be determined so as to achieve a desired viscosity for use.

[0088] In order to exhibit sufficient curability and workability of the curable resin composition, the mass ratio of the aforementioned polysiloxane resin to the aforementioned (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.

[0089] [Manufacturing method of (B) (meth)acrylic acid derivative]

[0090] The manufacturing method of the (meth)acrylic acid derivative of the present embodiment is not particularly limited, and it can be manufactured by a publicly known and commonly used method.

[0091] For example, a dehydration condensation reaction of (meth)acrylic acid with the corresponding hydroxy compound can be carried out, or a dehydrohalogenation reaction of (meth)acryloyl halide with the corresponding hydroxy compound can be carried out in the presence of a basic substance.

[0092] In the case of the dehydration condensation reaction, it can be obtained by the following method: using 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.), the reaction is carried out at a temperature preferably of 70 to 150 °C. With respect to 1 mol of the hydroxy compound, the usage ratio of (meth)acrylic acid is 1 to 5 mol, preferably 1.05 to 2 mol. With respect to the used (meth)acrylic acid, the esterification catalyst is present at a concentration of 0.1 to 15 mol%, preferably 1 to 6 mol%.

[0093] In addition, in the dehydrohalogenation reaction in the presence of a basic substance, for example, it can be obtained by reacting (meth)acryloyl chloride with the corresponding hydroxy compound. At this time, it is preferable to pre-add a basic substance such as triethylamine, pyridine, potassium hydroxide, or sodium hydroxide. At this time, it is preferable to pre-add a phase transfer catalyst such as benzyltributylammonium chloride, tetrabutylammonium bromide, or benzyltriethylammonium chloride. It can be obtained by the following method: in the presence of a solvent (e.g., toluene, benzene, cyclohexane, n-hexane, n-heptane, acetone, tetrahydrofuran, etc.) or water, (meth)acryloyl chloride is reacted with the corresponding hydroxy compound at a temperature preferably of -10 to 100 °C.

[0094] As for the aforementioned hydroxy compound, there is no particular limitation. For example, the following can be enumerated: hydroxybiphenyl; 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, dihydroxybiphenyl; 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 2,5-dihydroxybiphenyl, phenylbenzyl alcohol; 3-phenylbenzyl alcohol, 4-phenylbenzyl alcohol, benzylphenol; 2-benzylphenol, 3-benzylphenol, 4-benzylphenol, dihydroxyphenylmethane; 4,4'-dihydroxydiphenyldiphenylmethane, 2,2'-dihydroxydiphenyldiphenylmethane, 2,4'-dihydroxydiphenyldiphenylmethane, hydroxydiphenylmethyl; diphenylmethanol, diphenylethanol; 1,1-diphenylethanol, 2,2-diphenylethanol, 1,1-diphenyl-1,2-ethylene glycol, phenoxyphenol; 2-phenoxyphenol, 3-phenoxyphenol, 4-phenoxyphenol, dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 2,4'-dihydroxydiphenyl ether, phenoxybenzyl alcohol; 2-phenoxybenzyl alcohol, 3-phenoxybenzyl alcohol, 4-phenoxybenzyl alcohol, phenylphenoxyethanol; 2-phenylphenoxyethanol, 3-phenylphenoxyethanol, 4-phenylphenoxyethanol, naphthol; 1-naphthol, 2-naphthol, dihydroxynaphthalene; 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, naphthylmethanol; 1-naphthylmethanol, 2-naphthylmethanol, naphthalenedimethanol; 1,4-naphthalenedimethanol, 1,5-naphthalenedimethanol, 1,8-naphthalenedimethanol, 2,3-naphthalenedimethanol, trihydroxyphenylmethyl; tris(4-hydroxyphenyl)methane, trihydroxyphenylethane, 1,3,5-tris(4-hydroxyphenyl)benzene, tetrakis(4-hydroxyphenyl)methane, tetrahydroxyphenylethane; 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenylenedimethylene tetraphenol; α,α,α',α'-tetrakis(4-hydroxyphenyl)p-xylene, α,α,α',α'-tetrakis(4-hydroxyphenyl)m-xylene, 2,3,6,7,10,11-hexahydroxytriphenylene, and their isomers, etc.

[0095] <(C) Free radical polymerization initiator>

[0096] In the present embodiment, the free radical polymerization initiator is not particularly limited as long as it can initiate free radical polymerization by heating or irradiation with active light such as ultraviolet light or visible light. For example, the following can be enumerated: thermal free radical polymerization initiators, photo free radical polymerization initiators, etc.

[0097] Examples of the photo radical 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-diphenylethane-1-one, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, etc.

[0098] Examples of the commercially available products of these radical polymerization initiators include: "Irgacure-184", "rgacure-149", "rgacure-261", "rgacure-369", "rgacure-500", "rgacure-651", "rgacure-754", "rgacure-784", "rgacure-819", "rgacure-907", "rgacure-1116", "rgacure-1664", "rgacure-1700", "rgacure-1800", "rgacure-1850", "rgacure-2959", "rgacure-4043", "rgacure-1173" (manufactured by Ciba specialty chemicals), "Lucirin TPO" (manufactured by BASF), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stauffer Chemical), "Trigonal P1" (manufactured by Akzo), "Sandoray1000" (manufactured by Sandoz), "DEAP" (manufactured by UPJOHN), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), etc.

[0099] In order to exhibit sufficient curability, the aforementioned radical polymerization initiator is preferably in the range of 0.05 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, based on 100 parts by mass of the curable resin composition.

[0100] <Other components>

[0101] Furthermore, in the curable resin composition of the present embodiment, so-called additives such as a photosensitizer, an antioxidant, a surfactant, a leveling agent, a light stabilizer, and a filler can be added as needed in a proportion that does not adversely affect the effects of the present invention. When the components other than the essential components are 10 parts by mass or less with respect to 100 parts by mass of the curable resin composition, the effects of the present invention are particularly excellent, and thus it is preferred.

[0102] (Photosensitizer)

[0103] When curing the curable resin composition of the present embodiment by photopolymerization, various photosensitizers can be added in combination with the aforementioned radical polymerization initiator. Examples of the aforementioned photosensitizer include: amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, or other nitrogen-containing compounds, etc. They can be used alone or in combination of two or more. When adding these photosensitizers, the addition amount is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the curable resin composition.

[0104] (Antioxidant)

[0105] The curable resin composition of the present embodiment can also be added with an antioxidant for the purpose of improving heat resistance. Examples of the aforementioned antioxidant include hindered phenol compounds, hindered amine compounds, etc. When adding these antioxidants, the addition amount is preferably in the range of 0.01 to 1 part by mass with respect to 100 parts by mass of the curable resin composition.

[0106] (Surfactant)

[0107] The curable resin composition of the present embodiment can also be added with a surfactant for the purpose of improving coatability. Examples of the aforementioned surfactant include fluorine-based surfactants. Specifically, examples include: perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides, fluorine-containing organosiloxane compounds, etc. When adding these surfactants, the addition amount is preferably in the range of 0.01 to 1 part by mass with respect to 100 parts by mass of the curable resin composition.

[0108] (Light stabilizer)

[0109] As the aforementioned light stabilizer, commercially available substances can be used. For example, the following can be cited: TINUVIN (registered trademark) 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 770 [manufactured by BASF Japan Ltd.]; ADK STAB (registered trademark) LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA-82, ADK STAB LA-87 [manufactured by Adeka Corporation], etc.

[0110] 〔Preparation of curable resin composition〕

[0111] The method for preparing the curable resin composition of this embodiment is not particularly limited as long as it is a method for sufficiently mixing. Generally, stirring and mixing using a stirring blade is preferred. The stirring time and stirring speed can be appropriately determined according to the compounding amounts of the above-mentioned respective components. From the viewpoint of ensuring sufficient mixability, the stirring time can be 1 to 24 hours and the stirring speed can be 10 to 1,000 rpm.

[0112] From the viewpoints of improving coatability and transparency, the aforementioned curable resin composition is preferably filtered through a filter to remove foreign substances. In addition, it is preferable to remove bubbles in the curable resin composition using a defoaming device such as a vacuum pump.

[0113] The aforementioned curable resin composition preferably has a viscosity with excellent operability. For example, it is preferably in the range of 500 to 100,000 mPa·s at 25°C. In addition, it can also be diluted with an organic solvent as described later to prepare a desired viscosity.

[0114] 〔Curable resin varnish〕

[0115] For the purpose of improving coatability, the curable resin composition of the present embodiment can also be diluted with an organic solvent to form a curable resin varnish. As the aforementioned organic solvent, as long as it can dissolve the aforementioned curable resin composition, there is no particular limitation, and examples include: aromatic hydrocarbons, ethers, alcohols, ketones, esters, amides. Specifically, 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, N-methylpyrrolidone, etc. These can be used alone or in combination of two or more.

[0116] Since the curable resin composition of the present embodiment has low light absorption loss, high UV curability, and excellent workability, it is suitable for components used in optoelectronic hybrid substrates, optical waveguides, right-angle high-way converters, optical PINs, microlenses, spot size converters, optical shuffling sheets, optical converters, optical adhesives, etc.

[0117] 〔Optical waveguide〕

[0118] The method of forming an optical waveguide using the curable resin composition of the present embodiment can use a well-known and commonly used method. Generally, a curable resin layer can be formed on a substrate, and then an optical waveguide can be formed by performing exposure and development processes.

[0119] As the aforementioned substrate, there is no particular limitation, and examples include: silicon wafers, glass wafers, quartz wafers, plastic circuit boards, ceramic circuit boards, etc.

[0120] As a method for forming the curable resin layer, it can be formed by coating on a substrate using a spin coating method, dip coating method, spray coating method, bar coating method, roll coating method, curtain coating method, gravure coating method, screen coating method, inkjet coating method, etc. The coating amount can be appropriately selected according to the purpose. It should be noted that when using the aforementioned curable resin varnish, a drying treatment can also be performed after forming the curable resin layer as needed.

[0121] When curing the aforementioned curable resin layer by exposure, the exposure amount is preferably 0.01 to 10 J / cm 2If it is within the aforementioned range, curing can proceed sufficiently, and a fine pattern can be formed. At this time, it is preferable to perform exposure under light with a wavelength of 240 to 500 nm. As the light with a wavelength of 240 to 500 nm, various wavelengths of light generated by a radiation generating device can be cited, such as ultraviolet rays such as g-rays and i-rays, and far ultraviolet rays (248 nm).

[0122] After the exposure treatment, development is performed using a developer. The aforementioned developer is an organic solvent-based developer or an alkali developer, and they can also be used in combination.

[0123] As the aforementioned organic solvent-based developer, for example, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. can be cited.

[0124] As the aforementioned alkali developer, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal pyrophosphates, sodium salts, ammonium salts, organic salts, etc. can be used as the alkali.

[0125] Examples

[0126] The following examples of the present invention will be further specifically described, but the present invention is not limited to these examples.

[0127] 〔Evaluation method〕

[0128] <Evaluation of light absorption loss>

[0129] A curable resin composition is injected into a fluororubber O-ring provided on a glass plate, and it is clamped from above with a glass plate so as to avoid mixing of air bubbles. Under a nitrogen atmosphere, cumulative light is irradiated with a high-pressure mercury lamp at 3000 mJ / cm 2 , to form a cured product. The aforementioned cured product is peeled off from the glass plate and the O-ring, and a test piece with a diameter of 20 mm and a thickness of 5 mm is obtained.

[0130] Using an ultraviolet-visible-near-infrared spectrophotometer (V-670) manufactured by JASCO Corporation, the absorbance of the above test piece in the wavelength range of 400 to 2000 nm is measured. Since the reduction amount of the transmittance at 800 nm is consistent with the intensity of the reflected light, 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 850 nm, 1310 nm, and 1550 nm is calculated according to the following formula.

[0131] Light absorption loss (dB / cm) = absorbance × 2 × 10

[0132] The light absorption loss calculated according to the above formula is preferably 0.1 or less at 850 nm. It is preferably 0.4 or less at 1310 nm, and particularly preferably 0.2 or less. It is preferably 0.6 or less at 1550 nm, and particularly preferably 0.4 or less.

[0133] <Evaluation of heat resistance>

[0134] Using a TG-DTA device (TG-8120) manufactured by Rigaku Corporation, measurement was carried out under a nitrogen gas flow of 20 mL / min at a heating rate of 20 °C / min to measure the 5% weight loss temperature (Td5). The aforementioned Td5 is preferably 300 °C or higher, and particularly preferably 350 °C or higher.

[0135] <Evaluation of weight average molecular weight>

[0136] Measurement was carried out using the following measurement equipment and measurement conditions to measure the weight average molecular weight.

[0137] Measurement equipment: "HLC-8320GPC" manufactured by Tosoh Corporation

[0138] 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

[0139] Detector: RI (differential refractometer)

[0140] Data processing: "GPC WorkStation EcoSEC-WorkStation" manufactured by Tosoh Corporation

[0141] Measurement conditions: Column temperature 40 °C

[0142] Developing solvent: Tetrahydrofuran

[0143] Flow rate: 1.0 mL / min

[0144] Standard: According to the measurement manual of the aforementioned "GPC WorkStation EcoSEC-WorkStation", the following monodisperse polystyrene with known molecular weight was used.

[0145] (Polystyrene used)

[0146] "A-500" manufactured by Tosoh Corporation

[0147] "A-1000" manufactured by Tosoh Corporation

[0148] "A-2500" manufactured by Tosoh Corporation

[0149] "A-5000" manufactured by Tosoh Corporation

[0150] "F-1" manufactured by Tosoh Corporation

[0151] "F-2" manufactured by Tosoh Corporation

[0152] "F-4" manufactured by Tosoh Corporation

[0153] "F-10" manufactured by Tosoh Corporation

[0154] "F-20" manufactured by Tosoh Corporation

[0155] "F-40" manufactured by Tosoh Corporation

[0156] "F-80" manufactured by Tosoh Corporation

[0157] "F-128" manufactured by Tosoh Corporation

[0158] (Production Example 1)

[0159] In a 1 L flask equipped with a thermometer, a cooling tube, and a stirrer, 237.9 g (1.1 mol) of diphenylsilanediol, 124.2 g (0.5 mol) of 3-(methacryloyloxy)propyltrimethoxysilane, 99.1 g (0.5 mol) of phenyltrimethoxysilane, and 230.6 g of toluene were charged and heated to 50°C while stirring. Thereafter, 0.37 g of barium hydroxide monohydrate was added, and the reaction was carried out at 50°C for 20 hours. After the reaction was completed, the obtained reaction mixture was cooled to room temperature and filtered using a membrane filter with a pore size of 0.2 μm. Using a rotary evaporator, toluene and methanol as a by-product were removed under reduced pressure. A polysiloxane resin (A1) having a methacryloyl group with a weight-average molecular weight of 2900 was obtained.

[0160] (Production Example 2)

[0161] 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, and synthesis was carried out in the same manner as in Production Example 1 except for this, to obtain a polysiloxane resin (A2) having an acryloyl group with a weight-average molecular weight of 2900.

[0162] (Production Example 3)

[0163] 124.2 g (0.5 mol) of 3-(methacryloyloxy)propyltrimethoxysilane in Production Example 1 was changed to 112.2 g (0.5 mol) of trimethoxy(4-vinylphenyl)silane, and synthesis was carried out in the same manner as in Production Example 1 except for this, to obtain a polysiloxane resin (A3) having a styryl group with a weight-average molecular weight of 3000.

[0164] (Production Example 4)

[0165] Change 237.9 g (1.1 mol) of diphenylsilanediol in Production Example 1 to 194.7 g (0.9 mol) of diphenylsilanediol, and perform synthesis in the same manner as in Production Example 1 except for this, to obtain a polysiloxane resin (A4) having a methacryloyl group and a weight-average molecular weight of 2800.

[0166] (Production Example 5)

[0167] Change 237.9 g (1.1 mol) of diphenylsilanediol in Production Example 1 to 216.3 g (1.0 mol) of diphenylsilanediol, and perform synthesis in the same manner as in Production Example 1 except for this, to obtain a polysiloxane resin (A5) having a methacryloyl group and a weight-average molecular weight of 2800.

[0168] (Production Example 6)

[0169] Change 237.9 g (1.1 mol) of diphenylsilanediol in Production Example 1 to 302.8 g (1.4 mol) of diphenylsilanediol, and perform synthesis in the same manner as in Production Example 1 except for this, to obtain a polysiloxane resin (A6) having a methacryloyl group and a weight-average molecular weight of 3500.

[0170] (Production Example 7)

[0171] Change 237.9 g (1.1 mol) of diphenylsilanediol in Production Example 1 to 324.5 g (1.5 mol) of diphenylsilanediol, and perform synthesis in the same manner as in Production Example 1 except for this, to obtain a polysiloxane resin (A7) having a methacryloyl group and a weight-average molecular weight of 3900.

[0172] (Production Example 8)

[0173] Put 24.06 g (0.129 mol) of 4-phenoxyphenol, 96.23 g of dichloromethane, and 15.69 g (0.155 mol) of triethylamine into a 200 mL flask equipped with a thermometer, a condenser, and a stirrer, and cool to 0 °C with an ice bath while stirring. Thereafter, dropwise add 14.03 g (0.155 mol) of acryloyl chloride over 5 hours. Thereafter, return to room temperature of 25 °C and react for another 5 hours. Thereafter, stop stirring, and wash the reaction solution 10 times with pure water. Thereafter, distill off dichloromethane from the reaction solution under reduced pressure using an evaporator to obtain a liquid acrylic derivative (B1) represented by the following structural formula.

[0174]

[0175] (Production Example 9)

[0176] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 23.80 g (0.129 mol) of 4-benzylphenol. Otherwise, carry out the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B2) represented by the following structural formula.

[0177]

[0178] (Production Example 10)

[0179] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 21.99 g (0.129 mol) of o-phenylphenol. Otherwise, carry out the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B3) represented by the following structural formula.

[0180]

[0181] (Production Example 11)

[0182] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 23.80 g (0.129 mol) of [1,1'-biphenyl]-3-methanol. Otherwise, carry out the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B4) represented by the following structural formula.

[0183]

[0184] (Production Example 12)

[0185] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 25.87 g (0.129 mol) of 3-phenoxybenzyl alcohol. Otherwise, carry out the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B5) represented by the following structural formula.

[0186]

[0187] (Production Example 13)

[0188] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 27.68 g (0.129 mol) of o-phenylphenoxyethanol. Otherwise, carry out the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B6) represented by the following structural formula.

[0189]

[0190] (Production Example 14)

[0191] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 23.81 g (0.129 mol) of diphenylmethanol, and otherwise conduct the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B7) represented by the following structural formula.

[0192]

[0193] (Production Example 15)

[0194] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 25.62 g (0.129 mol) of 1,1-diphenylethanol, and otherwise conduct the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B8) represented by the following structural formula.

[0195]

[0196] (Production Example 16)

[0197] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 20.44 g (0.129 mol) of 1-naphthalenemethanol, and otherwise conduct the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B9) represented by the following structural formula.

[0198]

[0199] (Production Example 17)

[0200] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 12.03 g (0.0646 mol) of 2,2'-biphenol, and otherwise conduct the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B10) represented by the following structural formula.

[0201]

[0202] (Production Example 18)

[0203] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 13.84 g (0.0646 mol) of 1,1-diphenyl-1,2-ethanediol, and otherwise conduct the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B11) represented by the following structural formula.

[0204]

[0205] (Production Example 19)

[0206] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 12.16 g (0.0646 mol) of 1,5-naphthalenedimethanol. Otherwise, perform the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B12) represented by the following structural formula.

[0207]

[0208] (Production Example 20)

[0209] Change 14.03 g of acryloyl chloride in Production Example 8 to 16.20 g (0.155 mol) of methacryloyl chloride. Otherwise, perform the synthesis in the same manner as in Production Example 8 to obtain a liquid acrylic derivative (B13) represented by the following structural formula.

[0210]

[0211] (Production Example 21)

[0212] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 12.59 g (0.0431 mol) of tris(4-hydroxyphenyl)methane. Otherwise, perform the synthesis in the same manner as in Production Example 8 to obtain a solid acrylic derivative (B14) represented by the following structural formula.

[0213]

[0214] (Production Example 22)

[0215] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 12.87 g (0.0323 mol) of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Otherwise, perform the synthesis in the same manner as in Production Example 8 to obtain a solid acrylic derivative (B15) represented by the following structural formula.

[0216]

[0217] (Production Example 23)

[0218] Change 24.06 g of 4-phenoxyphenol in Production Example 8 to 15.96 g (0.0431 mol) of 1,3,5-tris(4-hydroxyphenyl)benzene. Otherwise, perform the synthesis in the same manner as in Production Example 8 to obtain a solid acrylic derivative (B16) represented by the following structural formula.

[0219]

[0220] (Production Example 24)

[0221] In Production Example 8, 24.06 g of 4-phenoxyphenol was changed to 12.42 g (0.0323 mol) of tetrakis(4-hydroxyphenyl)methane, and synthesis was carried out in the same manner as in Production Example 8 except for this, to obtain a solid acrylic derivative (B17) represented by the following structural formula.

[0222]

[0223] Using the polysiloxane resins (A1 to A7), acrylic derivatives (B1 to B15), and 2-hydroxy-2-methyl-1-phenylpropanone as a radical polymerization initiator obtained in the above production examples, curable resin compositions were prepared according to the formulations in Tables 1 to 3 and evaluated. The obtained curable resin compositions were liquid and had excellent workability. In addition, the cured products could all be sufficiently cured by UV irradiation.

[0224] In the comparative examples, divinylbenzene and benzyl acrylate were used in place of the component (B) ((meth)acrylic derivative) obtained in the above production examples.

[0225] [Table 1]

[0226]

[0227] [Table 2]

[0228]

[0229] [Table 3]

[0230]

[0231] In the table, HMPP is the abbreviation of 2-hydroxy-2-methyl-1-phenylpropanone, DVB is the abbreviation of divinylbenzene, and BZA is the abbreviation of benzyl acrylate.

Claims

1. A curable resin composition containing the following components (A) to (C) as essential components: (A) A polysiloxane resin having at least one reactive group selected from the group consisting of (meth)acryloyl group and styryl group; (B) A (meth)acrylic acid derivative having a structure represented by the following general formula (1); (C) A radical polymerization initiator, In the general formula (1), R1 is a hydrogen atom or a methyl group, Y is any one of a single bond, a methylene group or an oxyethylene group, Z is any one of the following general formulas (1-1) to (1-10), n represents 1 to 6. It should be noted that when n is 2 to 6, a plurality of R1 and Y are optionally the same or different, In the general formulas (1-1) to (1-10), R2 is a single bond, an oxygen atom or a methylene group, R3 is a hydrogen atom or a methyl group, and R4 represents a direct bond, a single bond or a phenyl group.

2. The curable resin composition according to claim 1, wherein, In the general formula (1), n is 1 or 2.

3. The curable resin composition according to claim 1 or 2, wherein, The mass ratio of the component (A) to the component (B) is 99:1 to 10:

90.

4. The curable resin composition according to any one of claims 1 to 3, wherein In the general formula (1), R1 is a hydrogen atom, and Y is a single bond or a methylene group.

5. The curable resin composition according to any one of claims 1 to 4, wherein, In the general formulas (1-1) and (1-4), R2 is a single bond or an oxygen atom.

6. The curable resin composition according to any one of claims 1 to 5, wherein, In the general formulas (1-2) and (1-7), R3 is a hydrogen atom.

7. The curable resin composition according to any one of claims 1 to 6, wherein, The component (A) contains the structural formulas represented by the following general formulas (2) and (3), In the general formulas (2) and (3), R4 represents an organic group having 1 to 12 carbon atoms, and R5 and R6 each independently represent a methyl group or a phenyl group.

8. The curable resin composition according to claim 7, wherein, In the component (A), the molar ratio of the general formula (2) to the general formula (3) is 1:0.9 to 1:1.5.

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