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
  • C08F290/02—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 end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/068—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
  • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
  • C08F222/1035—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate of aromatic trialcohols
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
  • C08F222/1045—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate of aromatic tetraalcohols
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
  • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
• • 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
  • C08F290/148—Polysiloxanes

Definitions

• the present invention relates to a polymerizable composition (hereinafter sometimes abbreviated as "resin”) and a cured product produced from the resin, which are useful for optical applications, such as optical waveguides that can be used in optical communication applications and optical integrated circuit applications, or optical adhesives, or transparent sealants, or related parts thereof.
• resin polymerizable composition
• cured product produced from the resin which are useful for optical applications, such as optical waveguides that can be used in optical communication applications and optical integrated circuit applications, or optical adhesives, or transparent sealants, or related parts thereof.
• optical interconnect This type of short-distance optical communication technology is called optical interconnect, and as a component of this technology, there has been active development of optical-electrical composite boards in which part of the copper electrical wiring on a printed wiring board is replaced with optical wiring using optical fiber or optical waveguides.
• 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 the molecule 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 the difference in linear expansion coefficient between the substrate and the film, and the need for reactive ion etching to perform patterning, which increases the number of steps and reduces productivity.
• An organic/inorganic hybrid material that has 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 that has 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 that has 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 that has 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 that has an organic reactive group and a siloxane skeleton has been reported as a material that
• polymer materials for optical waveguides are exposed to high-temperature solder flow during electrical circuit formation, so materials with excellent heat resistance are required.
• lead-free solder with a high melting point has recently come to be used from the perspective of environmental concerns, so there is an increasing demand for polymer materials for optical waveguides with higher heat resistance.
• the light-receiving and light-emitting elements that transmit and receive light via the optical waveguide of an optoelectronic composite board are sealed with a transparent optical adhesive to increase the reliability of the elements.
• a transparent optical adhesive is used to connect a light-receiving and light-emitting element such as a vertical cavity surface emitting laser (VCSEL) to the optical waveguide on the board, and then soldering is performed by reflow to connect the electrical wiring to the light-receiving and light-emitting element and to fix 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 that contains a liquid aliphatic epoxy compound and a specific aromatic epoxy compound
• Patent Document 4 a curable resin composition that contains a (meth)acrylic acid ester having an alicyclic hydrocarbon group
• the objective of the present invention is to provide a material that has low absorption (low optical absorption loss) in the near-infrared region used in optical communications, has excellent heat resistance, and produces a cured product with excellent productivity (UV curability), as well as an optical waveguide and optical adhesive made using said material.
• the present inventors conducted extensive research to solve the above problems. As a result, they discovered that a curable resin composition containing a specific (meth)acrylic acid derivative has low light absorption loss, high heat resistance, and excellent UV curing properties, which led to the completion of the present invention.
• the present invention is as follows.
• a curable resin composition comprising 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) a (meth)acrylic acid derivative having a structure represented by the following general formula (1): (In the above general formula (1), R 1 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 formulae (1-1) to (1-8), and n is 1 to 6.
• R2 represents a single bond, an oxygen atom or a methylene group
• R3 represents a hydrogen atom or a methyl group
• R4 represents a direct bond, a single bond or a phenyl group.
• a polysiloxane resin having a specific reactive group a (meth)acrylic acid derivative having a specific structure, and a radical polymerization agent, it is possible to provide a curable resin composition that has low light absorption loss, high heat resistance, excellent UV curing properties, and excellent handling properties.
• the curable resin composition of the present embodiment contains, as essential components, (A) a polysiloxane resin, (B) a (meth)acrylic acid derivative, and (C) a radical polymerization agent.
• the polysiloxane resin has one or more reactive groups selected from the group consisting of (meth)acryloyl groups and styryl groups.
• radical polymerizable groups it is particularly preferable to have the reactive groups from the viewpoint of UV curability.
• the (meth)acryloyl group means an acryloyl group or a methacryloyl group.
• the polysiloxane resin may have at least one of the reactive groups, may have two or more, or may have three or more.
• a (meth)acryloyl group is particularly excellent in UV curability
• a styryl group is particularly excellent in low light absorption loss, and is preferable.
• the ratio may be appropriately selected according to the desired physical properties, and may contain only one of the reactive groups or any of the reactive groups, and is not particularly limited. From the viewpoint of UV curability, it is more preferable for one molecular chain of the polysiloxane resin to have one or more of the reactive groups, and it is particularly preferable for one molecular chain of the polysiloxane resin to have two or more.
• the concentration of reactive groups is preferably 500 to 10,000 mmol/kg, as this provides sufficient curability.
• 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, p-styrylethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylcyclohexane ...
• diorganodialkoxysilanes such as xyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, or 3-(meth)acryloyloxypropylmethyldiethoxysilane; various chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3-(meth)acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, or diphenyldichlorosilane; tetraethoxysilane, tetramethoxysilane, diphenylsilanediol, and di-p-tolylsi
• R4 is an organic group having 1 to 12 carbon atoms
• R5 and R6 each independently represent a methyl group or a phenyl group
• the wavy line portion represents a bonding site.
• Examples of the organic group having 1 to 12 carbon atoms in R 4 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 saturated heterocyclic groups such as 3-pyrrolidinopropyl; aryl groups such as phenyl, which may have an alkyl substituent; aralkyl groups such as phenylmethyl and phenylethyl; and the
• the organic group may have an oxygen atom or an amide bond between the carbon atoms, and may further have a hydroxyl 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 formulae represented by the general formulae (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 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 reduced.
• 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 can be reduced, and further, the solidification of the polysiloxane resin can be suppressed, improving the handling properties 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. If it is 1,000 or more, the molecular weight is large and the cured product will be strong, while if it is 100,000 or less, when it is made into a curable resin composition, it will have good compatibility with the (meth)acrylic acid derivative described below and excellent handleability, which is preferable.
• the weight average molecular weight is a polystyrene-equivalent measured value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.
• the method for producing the polysiloxane resin in this embodiment is not particularly limited, and a known and commonly used condensation reaction can be used. Below, a method for producing 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 the method is not limited thereto.
• the condensation reaction between a compound containing the structural formula represented by the above general formula (2) and a compound containing the structural formula represented by the above general formula (3) is carried out in the presence of an acid or base catalyst.
• the acid catalyst may, for example, be 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 such acids include tetraisopropoxy titanium (titanium tetraisopropoxide), tetra-n-butoxy titanium, tetraisobutoxy titanium, te
• 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, 2-amino-2-methyl-1-propanol, etc.
• magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide, ammonium hydroxide, or 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, based on the total mass of the compound containing the structural formula represented by the general formula (2) above and the compound containing the structural formula represented by the general formula (3) above. If it is within the above range, the condensation reaction proceeds sufficiently, which is preferable.
• the condensation reaction may be carried out without a solvent or in the presence of a solvent, but it is preferable to carry out the reaction in the presence of a solvent in order to make the reaction system uniform.
• the reaction solvent may be any solvent that does not react with the raw materials, and examples of the solvent 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. Of these,
• condensation reaction is a dealcoholization condensation reaction
• the reaction temperature can be adjusted appropriately to obtain 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 carry out a purification process as necessary.
• the (meth)acrylic acid derivative is characterized by having a structure represented by the following general formula (1).
• R 1 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 formulae (1-1) to (1-6)
• n is 1 to 6.
• n is 2 to 6
• multiple R 1s and Ys may be the same or different.
• R2 is a single bond, an oxygen atom, or a methylene group
• R3 is a hydrogen atom or a methyl group
• R4 is a direct bond, a single bond, or a phenyl group. Note that the wavy line in the formula indicates the bonding site with Y.
• the wavy line portions are bonding sites with Y, but it is not necessary that all wavy line portions are bonded to Y, and it is sufficient that at least one Y is bonded to the wavy line portions.
• one or more (meth)acrylic acid derivatives are included, and since there are particularly excellent physical properties depending on the structure of Z, as described below, multiple (meth)acrylic acid derivatives can be used in combination as appropriate to achieve the desired physical properties.
• the (meth)acrylic acid derivative plays a role in diluting 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 aliphatic C-H bond concentration and suppressing absorption in the near infrared region.
• the viscosity of the (meth)acrylic acid derivative is reduced, and when the (meth)acrylic acid derivative is made into a curable resin composition, solidification of the curable resin composition can be suppressed.
• the R 1 may be a hydrogen atom or a methyl group, and is particularly preferably a hydrogen atom from the viewpoint of reducing light absorption loss.
• Y may be a single bond, a methylene group, or an oxyethylene group, but from the viewpoint of reducing light absorption loss, a single bond or a methylene group is particularly preferred.
• R1 and Y may be used without any particular limitation. From the viewpoint of reducing light absorption loss, however, it is particularly preferable that R1 is a hydrogen atom and Y is a single bond or a methylene group.
• the n represents an integer from 1 to 6, more preferably from 1 to 4, and particularly preferably 1 or 2. If the n is within the above range, when the resin composition is made, it will have low light absorption loss, high heat resistance, and excellent UV curing properties, which is preferable. In particular, if n is 1 or 2, the viscosity of the (meth)acrylic acid derivative will be particularly low and it will also have excellent handleability, which is preferable.
• Z is not particularly limited as long as it is any of the general formulas (1-1) to (1-10) above.
• the resulting curable resin composition has particularly excellent UV curability, which is preferable.
• Z is the general formula (1-2) or (1-5), it is preferable because it has particularly excellent compatibility with polysiloxane resins.
• the resulting curable resin composition has particularly excellent heat resistance, which is preferable.
• the resulting curable resin composition has particularly excellent heat resistance, which is preferable.
• R 2 in the formula 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.
• R 3 in the formula may be a hydrogen atom or a methyl group, and is particularly preferably a hydrogen atom from the viewpoint of reducing light absorption loss.
• R 4 in the formula may be a single bond or a phenyl group, and is particularly preferably a single bond from the viewpoint of solvent solubility.
• the resulting (meth)acrylic acid derivative when Z is any one of the general formulas (1-1) to (1-6), the resulting (meth)acrylic acid derivative is liquid, and is particularly preferred because it can be used as a solvent-free system that does not require dilution with a solvent when blended with a polysiloxane resin.
• the resulting (meth)acrylic acid derivative is solid, and it is preferable to dilute it with a solvent before use when blending it with a polysiloxane resin. It is also possible to use it as a solventless system by blending a (meth)acrylic acid derivative in which Z in the general formula (1) is any one of the general formulas (1-1) to (1-6) above with a polysiloxane resin.
• the blending ratio can be appropriately determined to achieve the desired viscosity.
• 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 dehydration condensation reaction between (meth)acrylic acid and the corresponding hydroxyl group-containing compound may be carried out, or a dehydrohalogenation reaction between (meth)acrylic acid halide and the corresponding hydroxyl group-containing compound may be carried out in the presence of a basic substance.
• the product can be obtained by reacting the product 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, using a known method.
• 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.
• a dehydrohalogenation reaction in the presence of a basic substance for example, (meth)acrylic acid chloride can be reacted with a corresponding 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.
• the hydroxyl group-containing compound is not particularly limited, but examples thereof 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-diphenylethanol, 1,1-diphenyl-1,2-ethanediol, phenoxyphenol; 2-phenoxyphenol, 3-phenoxyphenol, 4-phenoxyphenol, dihydroxydiphenylether; 4,4'-dihydroxydiphenylether, 2,2'-dihydroxydiphenylether, 2,4'-dihydroxydiphenylether, phenoxybenzyl alcohol; 2-phenoxybenzyl alcohol, 3-phenoxybenzyl alcohol, 4-phenoxybenzyl alcohol, phenylphenoxye ethanol; 2-phenylphenoxyethanol, 3-phenylphenoxyethanol, 4-phenylphenoxyethanol, naphthol; 1-naphthol, 2-naphthol, dihydroxynaphthalene; 1,2-dihydroxynaphthalene, 1,3-di
• the radical polymerization initiator is not particularly limited as long as it initiates radical polymerization by heating or irradiation with active light such as ultraviolet light 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 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, 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 as necessary in proportions that do not adversely affect the effects of the present invention. It is preferable that the components other than the essential components are 10 parts by mass or less relative to 100 parts by mass of the curable resin composition, since the effects of the present invention are particularly excellent.
• Photosensitizer When the curable resin composition of the present embodiment is cured by photopolymerization, various photosensitizers may be added together with 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 relative to 100 parts by mass of the curable resin composition.
• antioxidant may be added to the curable resin composition of the present 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 with respect to 100 parts by mass of the curable resin composition.
• a surfactant may be added to the curable resin composition of the present embodiment for the purpose of improving the coating property.
• the surfactant include fluorine-based surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide, fluorine-containing organosiloxane compounds, etc.
• the amount of addition 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.
• 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.], Adeka 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
• Adeka STAB registered trademark
• the method for preparing the curable resin composition of the present embodiment is not particularly limited as long as it is a method that can sufficiently mix the components, and generally, stirring and mixing using a stirring blade is preferred.
• the stirring time and stirring speed may be appropriately determined depending on the blending amounts of the above-mentioned components, and from the viewpoint of ensuring sufficient mixing, the stirring time may be 1 to 24 hours and the stirring speed may be 10 to 1,000 rpm.
• the curable resin composition From the viewpoint of improving the coatability and transparency of the curable resin composition, it is preferable to remove foreign matter using a filter. It is also preferable to remove air bubbles from the curable resin composition using a defoaming 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.
• the composition may be further diluted with an organic solvent as described below to adjust the viscosity to the desired level.
• the curable resin composition of the present embodiment may be diluted with an organic solvent to form a curable resin varnish in order to improve the coating property.
• the organic solvent is not particularly limited as long as it can dissolve the curable resin composition, and examples of the organic solvent include aromatic hydrocarbons, ethers, alcohols, ketones, esters, and amides.
• organic solvent 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 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 handling properties, and can therefore be suitably used 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.
• optical waveguide The method for forming an optical waveguide using the curable resin composition of the present embodiment can be a known and commonly used method.
• the optical waveguide can be formed by forming a curable resin layer on a substrate, and then performing 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 coating the substrate with a method such as spin coating, dip coating, spraying, 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.
• a drying process may be performed after the curable resin layer is formed, if necessary.
• the exposure amount is preferably 0.01 to 10 J/ cm2 . Within this range, curing proceeds sufficiently and a fine pattern can be formed.
• exposure is preferably performed with light having a wavelength of 240 to 500 nm.
• the light having a wavelength of 240 to 500 nm include light having various wavelengths generated by a radiation generating device, such as ultraviolet rays such as g-rays and i-rays, and far ultraviolet rays (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 be, for example, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal pyrophosphate, a sodium salt, an ammonium salt, or an organic salt as a base.
• the curable resin composition was poured into a fluororubber O-ring placed on a glass plate, and the glass plate was sandwiched from above to prevent air bubbles from being trapped.
• a high-pressure mercury lamp was used to irradiate the composition with an integrated light of 3000 mJ/ cm2 under a nitrogen atmosphere to obtain a cured product.
• the cured product was peeled off from the glass plate and the 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 region of 400 to 2000 nm was measured using a UV-Vis-NIR spectrophotometer (V-670) manufactured by JASCO Corporation. Since the decrease in light transmittance at 800 nm coincides with 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 from 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.
• Td5 5% weight loss temperature
• Production Example 2 A polysiloxane resin (A2) having an acryloyl group and a weight average molecular weight of 2,900 was obtained by synthesis 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.
• Curable resin compositions were prepared and evaluated according to the formulations in Tables 1 to 3 using the polysiloxane resins (A1 to A7) obtained in the above manufacturing examples, acrylic acid derivatives (B1 to B15), and 2-hydroxy-2-methyl-1-phenylpropanone as a radical polymerization agent.
• the obtained curable resin compositions were liquid and had excellent handleability. Furthermore, all of the cured products could be sufficiently cured by UV irradiation.
• HMPP is an abbreviation for 2-hydroxy-2-methyl-1-phenylpropanone
• DVB is an abbreviation for divinylbenzene
• BZA is an abbreviation for benzyl acrylate.

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• 2023
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