Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
  • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
  • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind

Definitions

• the present invention relates to a curable resin composition, a cured product obtained by curing the resin composition, and an optical waveguide that are useful as optical waveguides, optical adhesives, transparent encapsulants, or related components that can be used in optical applications such as optical communications and optical integrated circuits.
• optical signal transmission instead of electrical, is also becoming increasingly important in the internal wiring of devices.
• This type of short-distance optical communication technology is called optical interconnect, and active development is underway on optical-electrical composite boards, which replace some of the copper electrical wiring on printed circuit boards with optical wiring using optical fiber or optical waveguides.
• quartz-based materials have typically been 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.
• fluorinated polyimides that can be used as optical materials for optical waveguides have been reported (Patent Document 1).
• Patent Document 1 fluorinated polyimide-based materials have few CH groups in their molecules and have low absorption in the near-infrared region, they require baking at high temperatures, which can lead to problems such as cracks caused by stress resulting from differences in the linear expansion coefficients between the substrate and the film, and the need for reactive ion etching to perform patterning, which increases the number of processes and reduces productivity.
• An organic/inorganic hybrid material with 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).
• Patent Document 2 An organic/inorganic hybrid material with 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 An organic/inorganic hybrid material with 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 An organic/inorganic hybrid material with 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 An organic/inorganic hybrid material with an organic reactive group and a siloxane skeleton has been reported as a material that can be patterned by
• polymer materials for optical waveguides are exposed to high-temperature solder flow during electrical circuit formation, so they must have excellent heat resistance.
• lead-free solder with a high melting point due to environmental concerns, there is an increasing demand for polymer materials for optical waveguides with even higher heat resistance.
• the light-emitting and receiving elements that transmit and receive light via the optical waveguides of an optoelectronic composite substrate are sealed with a transparent optical adhesive to increase the reliability of the elements.
• a transparent optical adhesive is used to connect a light-emitting and receiving element such as a vertical cavity surface-emitting laser (VCSEL) to the optical waveguide on the substrate, and then soldering is performed by reflow to connect the electrical wiring to the light-emitting and receiving element and secure the element in place. Therefore, such optical adhesives are required to have the same performance as the materials used in optical waveguides.
• VCSEL vertical cavity surface-emitting laser
• Patent Document 3 a resin composition characterized by containing a liquid aliphatic epoxy compound and a specific aromatic epoxy compound
• the objective of the present invention is to provide a curable resin composition that exhibits low absorption (low optical absorption loss) in the near-infrared region used in optical communications, has excellent heat resistance, and can produce a cured product with excellent productivity (UV curability). Furthermore, the present invention aims to provide a cured product obtained by curing the curable resin composition, and an optical waveguide comprising the cured product.
• a curable resin composition containing a specific (meth)acrylic acid derivative has low light absorption loss, high heat resistance, and excellent UV curing properties, leading to the completion of the present invention.
• the present invention is as follows:
• a curable resin composition containing the following components (A) to (C) 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; and (B) one or more (meth)acrylic acid derivatives selected from the group consisting of compounds having a structure represented by the following general formula (1): (In the above general formula (1), R1 and R2 each independently represent a hydrogen atom, a methyl group, a phenyl group, a naphthyl group, or a trifluoromethyl group, or a cyclohexyl group or a fluorenyl group to which R1 and R2 are bonded, and the hydrogen atom bonded to the aromatic ring may optionally be substituted with a fluorine atom.) (C) Radical polymerization initiator
• a polysiloxane resin having a specific reactive group a (meth)acrylic acid derivative having a specific structure, and a radical polymerization initiator, it is possible to provide a curable resin composition that has low light absorption loss, high heat resistance, excellent UV curing properties, and excellent handleability.
• the curable resin composition of the present embodiment is characterized by containing (A) a polysiloxane resin, (B) a (meth)acrylic acid derivative, and (C) a radical polymerization initiator as essential components.
• the polysiloxane resin has one or more reactive groups selected from the group consisting of a (meth)acryloyl group and a styryl group.
• the reactive groups are particularly preferred from the viewpoint of UV curability.
• (meth)acryloyl group refers to an acryloyl group or a methacryloyl group.
• the polysiloxane resin may have at least one of the reactive groups, and may have two or more, or even three or more.
• (meth)acryloyl groups are particularly excellent in UV curing properties
• styryl groups are particularly excellent in low light absorption loss, making them preferable.
• the ratio can be selected appropriately depending on the desired physical properties, and the resin may contain only one of the reactive groups or any of the reactive groups, and is not particularly limited. From the perspective of UV curing properties, it is more preferable for the polysiloxane resin to have one or more of the reactive groups in one molecular chain, and it is particularly preferable for the resin to have two or more.
• a concentration of reactive groups in the polysiloxane resin of 500 to 10,000 mmol/kg is preferred, as this ensures sufficient curing.
• 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, decyltriethoxys
• organotrialkoxysilanes such as p-styrylmethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styrylmethoxysilane, p-styrylethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylcyclo
• diorganodialkoxysilanes such as xyldimethoxysilane, 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; tetraethoxysilane, tetramethoxysilane, diphenylsilanediol, and di-p-tolylsi
• R3 represents an organic group having 1 to 12 carbon atoms
• R4 and R5 each independently represent a methyl group or a phenyl group
• the wavy line represents a bonding site.
• Examples of the organic group having 1 to 12 carbon atoms in R3 include chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, and t-butyl; alkoxy groups such as methoxy and ethoxy; cyclic alkyl groups such as cyclohexyl and norbornanyl; 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 which may have an alkyl substituent; and aralkyl groups such as phenylmethyl and phenylethyl.
• the organic group may have an oxygen atom, an amide bond, or the like 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.
• the molar ratio of the structural formulas represented by the general formulas (2) and (3) is preferably within the range of 1:0.9 to 1:1.5, and particularly preferably within the range of 1:1 to 1:1.4.
• the molar ratio of the structural formula represented by the general formula (3) is 0.9 or greater, the amount of hydroxyl groups in the polysiloxane resin can be suppressed, reducing water absorption and reducing absorption in the near-infrared region.
• the molar ratio of the structural formula represented by the general formula (3) is 1.5 or less, the amount of unreacted hydroxyl groups in the polysiloxane resin is reduced and solidification of the polysiloxane resin is suppressed, improving handleability when preparing the curable resin composition, which is preferable.
• the weight-average molecular weight of the polysiloxane resin is preferably 1,000 to 100,000, and more preferably 1,500 to 50,000. A molecular weight of 1,000 or more results in a high molecular weight, making the cured product tough. A molecular weight of 100,000 or less results in good compatibility with the (meth)acrylic acid derivative described below when made into a curable resin composition, and excellent handling properties, making it preferable.
• the weight-average molecular weight is a polystyrene-equivalent measurement value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the elution solvent.
• the method for producing the polysiloxane resin in this embodiment is not particularly limited, and any known or commonly used condensation reaction can be used. Methods for producing a polysiloxane resin containing the structural formula represented by the general formula (2) and the structural formula represented by the general formula (3) are shown below, but the method is not limited thereto.
• the condensation reaction between a compound containing the structural formula represented by general formula (2) above and a compound containing the structural formula represented by general formula (3) above is carried out in the presence of an acid or base catalyst.
• the acidic catalyst examples 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,
• suitable acids include tetraisopropoxy titanium (titanium tetraisopropoxide), tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra-sec
• 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.
• magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, and triethylamine are particularly preferred.
• the amount of the catalyst used is preferably 0.001 to 10% by mass, and particularly preferably 0.01 to 1% by mass, relative to the total mass of the compound containing the structural formula represented by general formula (2) above and the compound containing the structural formula represented by general formula (3) above. Amounts within this range are preferred because the condensation reaction proceeds sufficiently.
• the condensation reaction can be carried out without or in the presence of a solvent, but is preferably carried out in the presence of a solvent to ensure a uniform reaction system.
• Reaction solvents that do not react with the raw materials are sufficient, and examples 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 these, toluene is preferred.
• NMP N-methyl-2
• condensation reaction is a dealcoholization condensation reaction
• the reaction temperature can be adjusted appropriately to achieve the desired molecular weight distribution, and is usually between 30 and 100°C.
• the reaction time can be adjusted appropriately, but is usually between 1 and 40 hours.
• 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 perform a purification process if necessary.
• the (meth)acrylic acid derivative is characterized in that it is one or more (meth)acrylic acid derivatives selected from the group consisting of compounds containing a structure represented by the following general formula (1):
• R1 and R2 each independently represent a hydrogen atom, a methyl group, a phenyl group, a naphthyl group, or a trifluoromethyl group, or a cyclohexyl group or a fluorenyl group to which R1 and R2 are bonded, and the hydrogen atom bonded to the aromatic ring may optionally be substituted with a fluorine atom.
• the (meth)acrylic acid derivative is preferably a compound containing a structure represented by the following general formulas (1-1) to (1-5).
• the curable resin composition of the present invention must contain a derivative represented by the general formula (1) above as the (meth)acrylic acid derivative (B), and preferably contains at least one derivative represented by any of the general formulas (1-1) to (1-5) above, but may contain two or more. Furthermore, the curable resin composition may contain, in addition to the derivatives represented by the general formulas (1-1) to (1-5) above, a (meth)acrylic acid derivative other than the derivatives represented by the general formulas (1-1) to (1-5) above.
• the (meth)acrylic acid derivative serves to dilute the highly viscous polysiloxane resin when preparing the curable resin composition, thereby improving the handleability of the curable resin composition.
• the (meth)acrylic acid derivative contains the structure represented by the above general formula (1), thereby reducing the concentration of aliphatic C-H bonds and suppressing absorption in the near-infrared region.
• 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.
• 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.
• a (meth)acrylic acid derivative can be obtained by carrying out a dehydration condensation reaction between (meth)acrylic acid and a hydroxy group-containing compound, or by carrying out a dehydrohalogenation reaction between a (meth)acrylic acid halide and a hydroxy group-containing compound in the presence of a basic substance.
• a (meth)acrylic acid derivative can be obtained by reacting an esterification catalyst such as p-toluenesulfonic acid or sulfuric acid with 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.), using a known method, at a temperature of preferably 70 to 150°C.
• the proportion of (meth)acrylic acid used is 1 to 5 mol, preferably 1.05 to 2 mol, per mol of the hydroxy group-containing compound.
• the esterification catalyst is present at a concentration of 0.1 to 15 mol%, preferably 1 to 6 mol%, relative to the (meth)acrylic acid used.
• (meth)acrylic acid derivatives can be obtained by reacting (meth)acrylic acid chloride with a hydroxyl group-containing compound.
• a basic substance such as triethylamine, pyridine, potassium hydroxide, or sodium hydroxide.
• 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 hydroxyl group-containing compound in the presence of a solvent (e.g., toluene, benzene, cyclohexane, n-hexane, n-heptane, acetone, tetrahydrofuran, etc.) or water, preferably at a temperature of -10 to 100°C.
• a solvent e.g., toluene, benzene, cyclohexane, n-hexane, n-heptane, acetone, tetrahydrofuran, etc.
• the hydroxy group-containing compound is not particularly limited, but examples include 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, bishydroxyphenylmethane; 4,4'-dihydroxydiphenyldiphenylmethane, 2,2'-dihydroxydiphenyldiphenylmethane , 2,4'-dihydroxydiphenyldiphenylmethane, hydroxydiphenylmethyl; diphenylmethanol, diphenylethanol; 1,1-diphenylethanol, 2,2-diphenyl
• 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.
• photoradical polymerization initiators 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.
• the radical polymerization initiator is preferably used in an amount ranging from 0.05 to 20 parts by mass, and more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the curable resin composition.
• 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, if necessary, in proportions that do not adversely affect the effects of the present invention.
• the amount of components other than the essential components is 10 parts by mass or less relative to 100 parts by mass of the curable resin composition, the effects of the present invention are particularly excellent, and this is preferred.
• 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.
• 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.
• a surfactant may be added to the curable resin composition of this embodiment for the purpose of improving coatability.
• the surfactant include fluorine-based surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide, and fluorine-containing organosiloxane compounds.
• 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.
• 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].
• TINUVIN registered trademark
• ADK STAB registered trademark
• the method for preparing the curable resin composition of this embodiment is not particularly limited as long as it is a method that can sufficiently mix the components, and stirring and mixing using a stirring blade is generally preferred.
• the stirring time and stirring speed can be determined appropriately depending on the blending amounts of the above-mentioned components, and 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.
• a filter In order to improve application properties and transparency, it is preferable to remove foreign matter from the curable resin composition using a filter. It is also preferable to remove air bubbles from the curable resin composition using a degassing device such as a vacuum pump.
• 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. It may also be further diluted with an organic solvent, as described below, to adjust to the desired viscosity.
• 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, ⁇ -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.
• the curable resin composition of this embodiment has low optical absorption loss, high UV curability, and excellent handleability, making it suitable for use in components used in optoelectronic hybrid boards, optical waveguides, right-angle high-path converters, optical pins, microlenses, spot size converters, optical shuffling sheets, optical converters, optical adhesives, etc.
• the optical waveguide can be formed by using the curable resin composition of the present embodiment in a known, commonly used manner.
• the optical waveguide can be formed by forming a curable resin layer on a substrate, followed by exposure and development treatment.
• the substrate is not particularly limited, and examples include silicon wafers, glass wafers, quartz wafers, plastic circuit boards, and ceramic circuit boards.
• the curable resin layer can be formed by applying it to the substrate using methods such as spin coating, dip coating, spraying, bar coating, roll coating, curtain coating, gravure coating, screen coating, and inkjet coating.
• the amount of coating can be selected appropriately depending on the purpose.
• a drying process may be performed after the curable resin layer is formed.
• the exposure dose is preferably 0.01 to 10 J/ cm2 . Within this range, curing proceeds sufficiently, allowing for the formation of a delicate pattern.
• exposure is preferably performed with light having a wavelength of 240 to 500 nm.
• light having a wavelength of 240 to 500 nm include light of various wavelengths generated by a radiation generator, such as ultraviolet light such as g-line and i-line, and far ultraviolet light (248 nm).
• the developer is an organic solvent-based developer or an alkaline developer, and these may be used in combination.
• organic solvent-based developer examples include isopropyl alcohol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
• 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.
• 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.
• the absorbance of the test piece was measured in the wavelength range of 400 to 2000 nm using a UV-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.
• Optical absorption loss (dB/cm) absorbance ⁇ 2 ⁇ 10
• the optical absorption loss calculated from the above formula is preferably 0.1 or less at 850 nm, preferably 0.4 or less, and particularly preferably 0.2 or less, at 1310 nm, and preferably 0.6 or less, and particularly preferably 0.4 or less, at 1550 nm.
• the 5% weight loss temperature (Td5) was measured using a TG-DTA apparatus (TG-8120) manufactured by Rigaku Corporation under a nitrogen flow of 20 mL/min at a temperature increase rate of 20°C/min.
• the Td5 is preferably 300°C or higher, and particularly preferably 350°C or higher.
• Production Example 2 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-(acryloxy)propyltrimethoxysilane, to obtain a polysiloxane resin (A2) having an acryloyl group and a weight average molecular weight of 2,900.
• A2 polysiloxane resin having an acryloyl group and a weight average molecular weight of 2,900.
• Curable resin compositions were prepared and evaluated according to the formulations in Table 1 using the above-mentioned polysiloxane resins (A1-A3), acrylic acid derivatives (B1-B5), and 2-hydroxy-2-methyl-1-phenylpropanone as the radical polymerization initiator (C).
• the units of blend amounts in Table 1 are "parts by mass.”
• HMPP stands for 2-hydroxy-2-methyl-1-phenylpropanone
• DVD stands for divinylbenzene
• BZA stands for benzyl acrylate.
• the resulting curable resin compositions of Examples 1-5 were liquid and had excellent handleability. Furthermore, all of the cured products obtained from the curable resin compositions of Examples 1-5 could be sufficiently cured by UV irradiation.
• the cured products obtained from the curable resin compositions of Examples 1 to 5 have lower propagation loss in the wavelength range of 850 to 1550 nm compared to the cured products obtained from the curable resin compositions of Comparative Examples 1 to 3, indicating lower absorption loss in the near-infrared region. Furthermore, the cured products obtained from the curable resin compositions of Examples 1 to 5 have higher 5% weight loss temperatures Td5 compared to the cured products obtained from the curable resin compositions of Comparative Examples 1 to 3, indicating superior heat resistance.

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