Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or 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, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/02—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen

Definitions

• the present invention relates to a composition and a cured product thereof. More specifically, the present invention relates to a composition containing an amino group-containing polysiloxane and a specific polymer, and a cured product obtained by curing the composition.
• the insulating film is required to have heat resistance during the manufacturing process and use of electrical and electronic devices. Furthermore, in flexible devices such as flexible displays, the demand for which is rapidly increasing, materials are required for insulating films that have high strength against deformation such as tension and bending, for example, high elongation. Conventionally, polyimide-based materials and the like have been proposed as insulating film materials for such electric/electronic devices (for example, Patent Documents 1 and 2).
• Patent Document 1 as a laminated polyimide film that covers a conductor in a multilayer insulated wire, only a laminated polyimide film having a dielectric constant of about 3.5 at a measurement frequency of 1 MHz, and 3.45 in the lowest example, is shown in the examples. Not yet.
• Patent Document 2 the physical properties of a cured coating film made of a thermosetting polyimide resin composition using a specific polyimide resin are shown in Table 3, etc., and the glass transition temperature (Tg) is shown. It's hard to say that it's sexual enough.
• Tg glass transition temperature
• the present invention has been made in view of the above problems, and an object of the present invention is to provide a composition capable of forming a cured product having a low dielectric constant, excellent heat resistance, and elongation.
• a composition comprising an amino group-containing polysiloxane (A) and a polymer (B) having a structural unit (U) derived from an unsaturated aliphatic dicarboxylic acid monoester.
• a composition according to [1] above further comprising inorganic particles.
• a cured product obtained by curing the composition described in [1] or [2] above.
• the cured product according to [3] above, wherein the cured product is an insulating film.
• the composition of the present invention contains an amino group-containing polysiloxane (A) and a polymer (B) having a structural unit (U) derived from an unsaturated aliphatic dicarboxylic acid monoester, the composition has a low dielectric constant, A cured product with excellent heat resistance and elongation can be formed. Therefore, the composition of the present invention can be preferably used for insulating film materials in various technical fields, including electrical and electronic devices that use high frequencies.
• (meth)acrylate means “acrylate” or “methacrylate”
• (meth)acrylic means “acrylic” or “methacrylic”
• (meth)acryloyl ” means “acryloyl” or “methacryloyl”.
• (Meth)acrylate is also sometimes referred to as (meth)acrylic acid ester.
• composition of the present disclosure is characterized by containing an amino group-containing polysiloxane (A) and a polymer (B) having a structural unit (U) derived from an unsaturated aliphatic dicarboxylic acid monoester.
• A amino group-containing polysiloxane
• B polymer having a structural unit (U) derived from an unsaturated aliphatic dicarboxylic acid monoester.
• the amino group-containing polysiloxane (A) in the composition of the present disclosure means that the main chain has a polysiloxane skeleton, and at least one of the silicon atoms constituting the polysiloxane skeleton contains an amino group. It means a polymer formed by bonding groups.
• the polysiloxane skeleton may have a linear structure, such as a branched structure, or a cyclic structure. Among these, a chain structure is preferred, and a linear structure is more preferred.
• the amino group-containing group is not particularly limited as long as it is an organic group containing an amino group. In the amino group-containing group, it is preferable that the amino group is bonded to the silicon atom constituting the polysiloxane skeleton via a divalent organic group.
• the amino group-containing group is preferably a hydrocarbon group containing an amino group as a substituent.
• the hydrocarbon group is preferably an alkyl group, an aryl group, or an aralkyl group, and more preferably an alkyl group.
• the amino group in the amino group-containing group may be any of a primary amino group, a secondary amino group, and a tertiary amino group.
• the amino group-containing group includes one or more of these. Among the amino groups, primary amino groups and secondary amino groups are preferred, and primary amino groups are more preferred.
• amino group-containing group examples include an amino group-containing group represented by the following general formula (1), an amino group-containing group represented by the following general formula (2), and an amino group-containing group represented by the following general formula (3). It is preferable that it is at least one selected from the group consisting of amino group-containing groups.
• -R a NH 2 (1) In general formula (1), R a is a divalent hydrocarbon group or a group represented by -ROR-, and the two R's are the same or different and are divalent hydrocarbon groups.
• -R a NHR b (2) In general formula (2), R a is a divalent hydrocarbon group or a group represented by -ROR-, and the two R's are the same or different and are divalent hydrocarbon groups.
• R b is a monovalent hydrocarbon group or a group represented by -ROR', R is a divalent hydrocarbon group, and R' is a monovalent hydrocarbon group. represent.) -R a NHR c NH 2 (3) (In general formula (3), R a and R c are the same or different and are a divalent hydrocarbon group or a group represented by -ROR-, and the two R's are the same or different represents a divalent hydrocarbon group.)
• the divalent hydrocarbon groups represented by R a , R c , and R in the above general formulas (1) to (3) include alkylene groups, arylene groups, aralkylene groups, and the like. Among these, an alkylene group is preferred, an alkylene group having 1 to 18 carbon atoms is more preferred, an alkylene group having 1 to 8 carbon atoms is even more preferred, and an alkylene group having 1 to 6 carbon atoms is even more preferred.
• Examples of the monovalent hydrocarbon group represented by R b and R' in the above general formula (2) include an alkyl group, an aryl group, an aralkyl group, and the like. Among these, an alkyl group is preferred, an alkyl group having 1 to 18 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 6 carbon atoms is even more preferred.
• the divalent hydrocarbon groups represented by R a , R c , and R and the monovalent hydrocarbon groups represented by R b and R' each have a substituent.
• the substituent is not particularly limited, but preferably includes, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydrophilic groups such as hydroxyl group and mercapto group.
• the bonding position of the amino group-containing group in the amino group-containing polysiloxane (A) is not particularly limited.
• the amino group-containing group may be bonded to a terminal silicon atom of the polysiloxane skeleton, may be bonded to a silicon atom other than the terminal, or may be bonded to a terminal silicon atom or a silicon atom other than the terminal. You can leave it there.
• One preferred form is form (1) in which an amino group-containing group is bonded to at least one terminal silicon atom of the polysiloxane skeleton.
• a particularly preferred form is one in which an amino group-containing group is bonded to each silicon atom at the two ends.
• Another preferred form is a form (2) in which an amino group-containing group is bonded to some or all of the silicon atoms other than the ends of the polysiloxane skeleton, so-called a form in which an amino group-containing group is bonded as a side chain in the polysiloxane skeleton.
• An example is a combined form.
• an amino group-containing group is bonded to at least one terminal silicon atom of the polysiloxane skeleton, and the silicon atom other than the terminal of the polysiloxane skeleton is A form in which an amino group-containing group is bonded to part or all of is also included.
• the content of amino groups in the amino group-containing polysiloxane (A) is not particularly limited, but from the viewpoint of mechanical strength of the cured product obtained from the composition of the present disclosure, the amino group equivalent is 300 to 20,000 g/mol. It is preferable that More preferably, it is 500 to 10,000 g/mol, and still more preferably 1,000 to 5,000 g/mol.
• a value obtained by a measuring method based on the method described in JIS K 2501:2003 JIS K 7237 can be adopted.
• the amino group equivalent can be specifically determined by the method described below, and it is preferable to use the value obtained by the method described below.
• the amino group equivalent can be determined by calculating the number of moles of amino groups per unit mass from the total amine value and taking the reciprocal.
• the weight average molecular weight of the amino group-containing polysiloxane (A) is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably from 100 to 1,000,000, more preferably from 500 to 500,000, even more preferably is 1000 to 100000.
• the above weight average molecular weight can be measured by GPC (gel permeation chromatography) using a high-speed GPC device HLC-8320GPC (manufactured by Tosoh Corporation) using polystyrene as a standard substance and a 1mM triethylamine-tetrahydrofuran solution as an eluent. It can be measured by GPC (gel permeation chromatography) using TSKgel SuperHZ4000 and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation) as columns.
• atoms or functional groups other than the oxygen atom and the amino group-containing group constituting the siloxane bond are bonded to some or all of the silicon atoms constituting the polysiloxane skeleton. It is preferable.
• functional groups are preferred. Examples of the above atoms include hydrogen atoms and halogen atoms, with halogen atoms being preferred.
• the functional group include a hydroxyl group and an organic group. Examples of the organic group include a hydrocarbon group and an alkoxy group, which may have a substituent.
• the hydrocarbon group is preferably an alkyl group, an aryl group, or an aralkyl group, more preferably an alkyl group or an aryl group, even more preferably a methyl group or a phenyl group, and particularly preferably a methyl group.
• the organic group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
• the above atoms or functional groups are bonded to all silicon atoms among the silicon atoms constituting the polysiloxane skeleton.
• each silicon atom other than the silicon atom to which the amino group-containing group is bonded has a total of 2 or 3 atoms or functional groups other than the above amino group-containing group.
• they are bonded.
• the atoms or functional groups bonded to the silicon atoms constituting the polysiloxane skeleton may be the same or different.
• a particularly preferred form of the polysiloxane skeleton is a structure in which two methyl groups are bonded to each silicon atom constituting the polysiloxane skeleton (however, two methyl groups are bonded to the terminal silicon atom). structure in which two or three atoms are bonded), and has a dimethylpolysiloxane skeleton.
• a particularly preferred form of the above amino group-containing polysiloxane (A) is one having the above dimethylpolysiloxane skeleton, with amino group-containing groups bonded to both ends of the skeleton.
• the method for producing the amino group-containing polysiloxane (A) is not particularly limited, and can be produced by conventionally known methods.
• the amino group-containing polysiloxane (A) can be obtained by hydrolyzing and condensing an alkoxysilane compound having an amino group-containing group in a hydrous alcohol in the presence of an acid catalyst.
• an acid catalyst it is possible to hydrolyze and condense only one or more alkoxysilane compounds having an amino group-containing group, one or more alkoxysilane compounds having an amino group-containing group and an amino group-containing group may be used. It is preferable to co-hydrolyze and condense one or more alkoxysilane compounds other than the alkoxysilane compound having (hereinafter also referred to as other alkoxysilane compounds).
• alkoxysilane compounds having an amino group-containing group examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N- Trialkoxysilane compounds such as phenyl-3-aminopropyltrimethoxysilane, (N-phenylamino)methyltrimethoxysilane, diethylaminomethyltriethoxysilane; 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, Examples include dialkoxysilane compounds such as N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane. Among them, dialkoxysilane compounds are preferred.
• alkoxysilane compounds mentioned above include, but are not particularly limited to, tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane; Trialkoxysilane compounds such as methoxysilane, benzyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane; dimethyldimethoxysilane, methylphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, 3-glycidoxypropylmethyl Examples include dialkoxysilane compounds such as dimethoxysilane, (3-mercaptopropyl)methyldimethoxys
• amino group-containing polysiloxane (A) used in the composition of the present disclosure commercially available products can be used.
• commercially available products known as amino-modified silicones are preferred.
• Preferred commercial products include, for example, KF-8008, KF-8010, KF-8012, X-22-161A, X-22-161B, X-22-1660B-3, X-22-9409, KF-864, KF-865, KF-868, KF-859, KF-860, KF-880, KF-393, KF-8004, KF-8002, KF-8005, KF-867, KF-8021, KF-869, KF- 861 (manufactured by Shin-Etsu Chemical Co., Ltd.), DOWSIL BY 16-853U, DOWSIL BY 16-871, DOWSIL BY 16-879B, DOWSIL BY 16-892 (manufactured by Dow-Toray Industries, Inc.), and the like.
• Polymer (B) having structural unit (U) derived from unsaturated aliphatic dicarboxylic acid monoester a structural unit (U) derived from an unsaturated aliphatic dicarboxylic acid monoester is simply referred to as a "structural unit (U)", and has a structural unit (U) derived from an unsaturated aliphatic dicarboxylic acid monoester.
• Polymer (B) may also be simply referred to as “polymer (B).”
• the polymer (B) has a structural unit (U) derived from an unsaturated aliphatic dicarboxylic acid monoester as a structural unit.
• the unsaturated aliphatic dicarboxylic acid is not particularly limited, and examples thereof include maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentenioic acid, methylenesuccinic acid, 2,4-hexadienioic acid, acetylene dicarboxylic acid, etc.
• Preferred examples include unsaturated aliphatic dicarboxylic acids having 4 to 6 carbon atoms. Among them, maleic acid is more preferred. One or more of these can be used.
• the unsaturated aliphatic dicarboxylic acid monoester is not particularly limited, and examples thereof include monoalkyl esters and monoaryl esters of the unsaturated aliphatic dicarboxylic acid. These can be obtained, for example, by reacting an unsaturated aliphatic dicarboxylic acid or an unsaturated aliphatic dicarboxylic acid anhydride with a compound containing a hydroxy group such as alcohol or phenol. Among these, monoalkyl esters are preferred.
• the alkyl group in the monoalkyl ester is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and preferably an alkyl group having 1 to 8 carbon atoms. is more preferred, and an alkyl group having 1 to 6 carbon atoms is particularly preferred.
• the polymer (B) is preferably a polymer having a plurality of the above structural units (U) as structural units, and is also preferably a polymer having the above structural units (U) as repeating units. It is more preferable that the polymer (B) is a polymer having a plurality of the above structural units (U) as repeating units.
• the polymer (B) may be a polymer having only the structural unit (U) as a structural unit, but preferably further has other structural units.
• Other structural units are not particularly limited, but are preferably structural units derived from polymerizable monomers having ethylenically unsaturated double bonds, and among them, structural units derived from unsaturated aliphatic dicarboxylic acids, unsaturated More preferred are structural units derived from saturated aliphatic dicarboxylic acid anhydrides, structural units derived from styrene monomers, and structural units derived from (meth)acrylic monomers.
• the polymer (B) preferably has one or more of these as other structural units.
• the unsaturated aliphatic dicarboxylic acids are as described above, and are preferably unsaturated aliphatic dicarboxylic acids having 4 to 6 carbon atoms, with maleic acid being more preferred, and containing one or more of these. It is preferable.
• the unsaturated aliphatic dicarboxylic acid anhydride the above-mentioned preferred unsaturated aliphatic dicarboxylic acid anhydrides are preferably mentioned, and it is preferable to include one or more of these.
• styrenic monomer is not particularly limited, but examples include styrene, ⁇ -methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, 2-styrylethyltrimethoxysilane, and the like. , it is preferable to include one or more of these.
• Styrenic monomers have functional groups such as alkyl groups such as methyl groups and tert-butyl groups, nitro groups, nitrile groups, alkoxy groups, acyl groups, sulfone groups, hydroxy groups, and halogen atoms on the benzene ring. It may be.
• a polyfunctional styrene monomer can also be used as the styrene monomer.
• Preferred examples of the polyfunctional styrenic monomer include divinylbenzene. Styrene is particularly preferred as the styrenic monomer.
• the above-mentioned (meth)acrylic monomer is not particularly limited, and includes conventionally known (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, (meth)acrylonitrile, etc. It is preferable to include one species or two or more species.
• As the (meth)acrylic ester a polyfunctional (meth)acrylate can also be used.
• As the (meth)acrylic monomer (meth)acrylic acid is preferable.
• the polymer (B) preferably has a structural unit derived from a styrene monomer as the other structural unit, and particularly preferably has a structural unit derived from styrene.
• a structural unit derived from a styrene monomer curing shrinkage during curing tends to be suppressed.
• the polymer (B) preferably has as a structural unit a structural unit (U) derived from an unsaturated aliphatic dicarboxylic acid monoester and another structural unit, and the structural unit It is more preferable that the polymer has (U) and a structural unit derived from a (meth)acrylic monomer and/or a structural unit derived from a styrene monomer.
• a polymer having a structural unit derived from styrene is more preferable, and a polymer having the structural unit (U) and a structural unit derived from styrene is particularly preferable.
• the content of the structural unit (U) in the polymer (B) is preferably 20 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of all structural units constituting the polymer.
• the lower limit is more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more.
• the upper limit is more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less. That is, the content of the structural unit (U) is preferably 20 to 100 parts by mass, 25 to 80 parts by mass, and 30 to 70 parts by mass, based on 100 parts by mass of all structural units of the polymer (B). Part by mass.
• the ratio of the structural unit (U) and the other structural unit in the polymer (B) is not particularly limited, but the ratio of the structural unit (U) to 100 parts by mass of the other structural unit is 20 parts by mass or more. , preferably 500 parts by mass or less.
• the lower limit is more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more.
• the upper limit is more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. That is, the ratio of the structural unit (U) to 100 parts by mass of the above other structural units is preferably 20 to 500 parts by mass, more preferably 25 to 400 parts by mass, and even more preferably 30 to 300 parts by mass. be.
• the content of the structural unit derived from the styrene monomer in the polymer (B) is preferably 0 to 80 parts by mass, and preferably 20 to 80 parts by mass, based on 100 parts by mass of all structural units constituting the polymer. It is more preferably 75 parts by mass, and even more preferably 30 to 70 parts by mass.
• the content of the structural unit derived from the (meth)acrylic monomer in the polymer (B) is preferably 0 to 80 parts by mass based on 100 parts by mass of all structural units constituting the polymer. , more preferably 20 to 75 parts by weight, and still more preferably 30 to 70 parts by weight.
• the content of the structural unit derived from the unsaturated aliphatic dicarboxylic acid in the polymer (B) is preferably 0 to 80 parts by mass, and 20 parts by mass, based on 100 parts by mass of all structural units constituting the polymer.
• the amount is more preferably 75 parts by weight, and even more preferably 30 to 70 parts by weight.
• the content of the structural unit derived from the unsaturated aliphatic dicarboxylic acid anhydride in the polymer (B) is preferably 0 to 90 parts by mass based on 100 parts by mass of all structural units constituting the polymer. , more preferably 20 to 85 parts by weight, and still more preferably 30 to 80 parts by weight.
• the above polymer (B) includes the above structural unit (U), a structural unit derived from an unsaturated aliphatic dicarboxylic acid, a structural unit derived from an unsaturated aliphatic dicarboxylic acid anhydride, and a structure derived from a styrene monomer. It may further have another structural unit other than the unit and the structural unit derived from the (meth)acrylic monomer.
• the content thereof is preferably 10 parts by mass or less, and 7 parts by mass, based on 100 parts by mass of all structural units constituting the polymer. It is more preferably at most 5 parts by mass, and even more preferably at most 5 parts by mass.
• the structural unit (U) derived from the unsaturated aliphatic dicarboxylic acid monoester has a carboxy group (COOH) and/or a carboxylate salt (COOM), and preferably has a carboxy group.
• the unesterified carboxy group of the unsaturated aliphatic dicarboxylic acid in the structural unit (U) contained in the polymer (B) is a carboxy group or a salt thereof, but preferably a carboxy It is the basis.
• the polymer (B) preferably contains a structural unit (U) having a carboxyl group as the structural unit (U).
• the proportion of the structural unit (U) having a carboxyl group in the polymer (B) is not particularly limited, but is preferably 50 moles or more based on 100 moles of the total amount of structural units (U) contained in the polymer (B). More preferably 80 moles or more, particularly preferably 100 moles.
• the carboxy group equivalent of the polymer (B) is not particularly limited, but is preferably 100 to 500 g/mol.
• the lower limit is more preferably 125 g/mol or more, and even more preferably 150 g/mol or more.
• the upper limit is more preferably 450 g/mol or less, and even more preferably 400 g/mol or less. That is, the carboxy group equivalent of the polymer (B) is more preferably 125 to 450 g/mol, and still more preferably 150 to 400 g/mol.
• a value obtained by a measuring method based on the method described in JIS K 2501:2003 can be adopted.
• the carboxyl group equivalent can be determined by the method described below, and it is preferable to use the value obtained by the method described below.
• Method for measuring carboxy group equivalent Accurately weigh the amount of sample whose acid value is to be measured, dissolve it in a titration solvent, immerse a glass electrode and a reference electrode, and titrate with a 0.1 mol/L 2-propanolic potassium hydroxide standard solution. Plot the relationship between the readings of the potentiometer or pH meter and the corresponding titration of the 2-propanolic potassium hydroxide standard solution, and use the inflection point obtained on the titration curve as the end point. The total acid value is calculated by the amount of 0.1 mol/L 2-propanolic potassium hydroxide standard solution consumed.
• the carboxy group equivalent can be determined by calculating the number of moles of carboxy groups per unit mass from the total acid value and taking the reciprocal.
• the molecular weight of the polymer (B) is not particularly limited, but from the viewpoint of mechanical strength and solvent solubility, the weight average molecular weight is preferably 3,000 to 120,000. From the viewpoint of mechanical strength, the lower limit of the weight average molecular weight is more preferably 4,000 or more, even more preferably 5,000 or more, and the upper limit is more preferably 100,000 or less, even more preferably from the viewpoint of solvent solubility. is less than 80,000. That is, the weight average molecular weight of the polymer (B) is more preferably 4,000 to 100,000, and even more preferably 5,000 to 80,000.
• the above weight average molecular weight can be measured by GPC (gel permeation chromatography) using a high-speed GPC device HLC-8320GPC (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent, and using TSKgel SuperHZ as a column. -N (manufactured by Tosoh Corporation), it can be measured by GPC (gel permeation chromatography) method.
• the method for producing the polymer (B) is not particularly limited, and it can be produced by conventionally known polymerization methods such as solution polymerization, emulsion polymerization, and suspension polymerization. Among these, a method using solution polymerization is preferred.
• a monomer composition containing at least an unsaturated aliphatic dicarboxylic acid monoester is subjected to radical polymerization in a single or mixed solvent such as an ether such as dioxane, a hydrocarbon such as toluene, or a ketone such as acetone.
• a polymer (B) having a structural unit (U) can be obtained by carrying out a radical polymerization reaction using an initiator.
• the monomer composition may consist only of one or more unsaturated aliphatic dicarboxylic acid monoesters, or may further include unsaturated aliphatic dicarboxylic anhydrides, unsaturated aliphatic dicarboxylic acid anhydrides, and unsaturated aliphatic dicarboxylic acid monoesters. , (meth)acrylic monomers, styrene monomers, and other monomers that serve as raw materials for the other structural units mentioned above.
• a monomer composition containing at least an unsaturated aliphatic dicarboxylic acid anhydride is used instead of a monomer composition containing at least an unsaturated aliphatic dicarboxylic acid monoester, and in the same manner as above, After obtaining a polymer (b) having a structural unit derived from an unsaturated aliphatic dicarboxylic acid anhydride by a radical polymerization reaction, in order to convert a part or all of the structural unit into a structural unit (U). Polymer (B) can be obtained by performing an esterification reaction.
• the monomer composition in this case may consist only of one or more unsaturated aliphatic dicarboxylic acid anhydrides, and may further include (meth)acrylic monomers, styrene monomers, etc. It may also contain monomers that serve as raw materials for the other structural units mentioned above, such as bodies.
• Examples of the esterification reaction include a method in which the polymer (b) is reacted with a compound containing a hydroxyl group such as alcohol or phenol.
• a monomer composition containing at least an unsaturated aliphatic dicarboxylic acid is used instead of a monomer composition containing at least an unsaturated aliphatic dicarboxylic acid anhydride, and radical polymerization is carried out in the same manner as above.
• a polymer (b) having a structural unit derived from an unsaturated aliphatic dicarboxylic acid is obtained, and then an esterification reaction is performed to convert some or all of the structural units into the structural unit (U).
• Polymer (B) can also be obtained by performing the following steps.
• a commercially available product may be used as it is, or a commercially available acid anhydride may be esterified.
• commercially available products of the polymer (B) include Alastair 700 (manufactured by Arakawa Chemical Industries, Ltd.), XIRAN1440, XIRAN2625, XIRAN17352, XIRAN3840 (manufactured by POLYSCOPE), and one or more of these Two or more types can be preferably used.
• polymers containing structural units derived from acid anhydrides of unsaturated aliphatic dicarboxylic acids include XIRAN1000, XIRAN2000, XIRAN2500, XIRAN3000, XIRAN3500, XIRAN3600, XIRAN4000, XIRAN6000, , EF30, EF40, Examples include EF41, EF61, EF80 (manufactured by POLYSCOPE), and monoesterification of one or more of these can be used as the polymer (B).
• the blending ratio of the amino group-containing polysiloxane (A) and the polymer (B) is not particularly limited; (B) contains the amino group-containing polysiloxane (A) and the polymer (B) so that the proportion of the structural unit (U) in the molar ratio is 1/3 to 3/1. is preferred.
• the molar ratio is more preferably 1/2 to 2/1, and even more preferably 1/1.
• the ratio of the carboxy groups possessed by the polymer (B) to the amino groups possessed by the amino group-containing polysiloxane (A) is the same as the above molar ratio.
• the total content of the amino group-containing polysiloxane (A) and the polymer (B) in the composition of the present disclosure is not particularly limited, but is 5 to 100 parts by mass based on 100 parts by mass of the composition of the present disclosure. It is preferably 10 to 80 parts by weight, still more preferably 15 to 70 parts by weight, and particularly preferably 20 to 60 parts by weight.
• the content of the amino group-containing polysiloxane (A) in the composition of the present disclosure is not particularly limited, but is preferably from 1 to 70 parts by mass based on 100 parts by mass of the composition of the present disclosure.
• the amount is more preferably 5 to 60 parts by weight, and even more preferably 10 to 50 parts by weight.
• the composition of the present disclosure may contain a solvent in addition to the amino group-containing polysiloxane (A) and the polymer (B).
• the above solvent is not particularly limited.
• polar substances such as water, alcohols, glycols, glycol derivatives, ethers, esters, ketones, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, ⁇ -butyrolactone, etc.
• Solvent examples include hydrocarbon solvents. One or more of these can be used. Among these, it is preferable to include a polar solvent and a hydrocarbon solvent.
• glycols are preferred, and glycol derivatives are more preferred.
• the alcohols mentioned above are not particularly limited, but methanol, ethanol, isopropyl alcohol, 1-propanol, 1-butanol, cyclohexanol and the like are preferred.
• the above-mentioned glycols are not particularly limited, but ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, etc. are preferable.
• glycol derivatives are not particularly limited, but include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , glycol monoalkyl ethers such as propylene glycol monobutyl ether; glycol monoacetates such as ethylene glycol monoacetate and propylene glycol monoacetate; ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate.
• glycol monoalkyl ethers are preferred.
• the hydrocarbon solvent is not particularly limited, but includes, for example, aliphatic hydrocarbons such as 1-hexane, 1-heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; and terpenes such as limonene. .
• aromatic hydrocarbons and terpenes are preferred, and terpenes are more preferred.
• the content of the solvent in the composition of the present disclosure is not particularly limited, but for example, the total content of the amino group-containing polysiloxane (A) and the polymer (B) in the composition of the present disclosure is 100% by mass.
• the amount is preferably 25 to 400 parts by mass. More preferably, it is 50 parts by mass or more, and still more preferably 70 parts by mass or more.
• the upper limit is more preferably 250 parts by mass or less, and even more preferably 150 parts by mass or less. That is, the content of the solvent is more preferably 50 to 250 parts by mass, and even more preferably The amount is 70 to 150 parts by mass.
• the composition of the present disclosure contains a solvent within the above range, when the composition of the present disclosure is used as a coating composition, a film with excellent film thickness uniformity can be easily obtained.
• Compositions of the present disclosure can contain inorganic particles.
• the inorganic particles preferably have a low dielectric constant, and preferably have a dielectric constant of 4.0 or less at 10 GHz. More preferably it is 3.5 or less, still more preferably 3.0 or less.
• the lower limit is not particularly limited, but is, for example, 0.5 or more. That is, the dielectric constant of the inorganic particles at 10 GHz is preferably 0.5 to 4.0, more preferably 0.5 to 3.5, and even more preferably 0.5 to 3.0.
• the above dielectric constant can be determined as follows.
• Method for measuring dielectric constant of inorganic particles Using a cell filled with inorganic particles as a measurement sample, the dielectric constant is measured at a frequency of 10 GHz using the cavity resonator perturbation method.
• the atmosphere at the time of measurement was a temperature of 25° C. and a humidity of 50%.
• the above measurement sample was obtained by cutting a polytetrafluoroethylene tube into a length of 10 cm, filling one side with 3 to 5 mm of sealing tape to create a tightly sealed cell, and filling the cell with inorganic particles.
• the filling rate of the inorganic particles is calculated from the true density, weight, and volume of the inorganic particles, and the dielectric constant of the inorganic particles is determined using the measurement result using a cell not filled with inorganic particles as a blank.
• the inorganic particles may be crystalline or amorphous in terms of X-ray diffraction, but are preferably amorphous.
• the structure of the inorganic particles is not particularly limited, and may be a porous structure or a dense structure. It may also have a hollow shape.
• the shape of the inorganic particles is not particularly limited and may be amorphous, granular, plate-like, columnar, acicular, etc., but granular is preferable, and among granules, spherical is preferable. Note that the above-mentioned granular shape means a uniform shape with an aspect ratio of 1.5 or less.
• the inorganic particles preferably have organic groups introduced onto their surfaces. By introducing an organic group, the dispersibility of the inorganic particles in the composition of the present disclosure tends to be excellent.
• organic groups include, but are not particularly limited to, hydrocarbon groups such as alkyl groups and aryl groups, (meth)acrylic groups, vinyl groups, and amino groups, among which aryl groups and (meth)acrylic groups are mentioned. preferable.
• the method for introducing an organic group onto the surface of the inorganic particles is not particularly limited, but a method of reacting the silane coupling agent having the organic group, a compound having a phosphoric acid group, or alcohol onto the surface of the inorganic particles is preferred. Examples include a method of reacting with hydroxyl groups or alkoxy groups present on the surface of inorganic particles.
• the average particle diameter of the inorganic particles is not particularly limited, but is preferably in the range of 1 nm to 1000 nm. When the average particle diameter of the inorganic particles is within the above range, a thin film with excellent homogeneity of physical properties such as dielectric constant tends to be easily obtained.
• the average particle diameter of the inorganic particles is more preferably 100 nm or less, even more preferably 50 nm or less, and particularly preferably 20 nm or less. More preferably, the lower limit is 5 nm or more. That is, the average particle diameter of the inorganic particles is more preferably 5 to 100 nm, still more preferably 5 to 50 nm, particularly preferably 5 to 20 nm.
• the above-mentioned average particle diameter is determined by observing the above-mentioned inorganic particles with a SEM (magnification of 1000 to 100,000 times, preferably 10,000 times) and analyzing the obtained image to determine the size of about 10 to 1000 individual particles ( It can be determined by determining the particle diameter (diameter equivalent to circular area) of the primary particles) and evaluating the 50% particle diameter in the number-based particle size distribution.
• SEM magnification of 1000 to 100,000 times, preferably 10,000 times
• analyzing the obtained image to determine the size of about 10 to 1000 individual particles ( It can be determined by determining the particle diameter (diameter equivalent to circular area) of the primary particles) and evaluating the 50% particle diameter in the number-based particle size distribution.
• known image analysis software for example, Mac-View manufactured by Mountech
• the material constituting the inorganic particles examples include inorganic oxides, inorganic nitrides, inorganic carbides, inorganic sulfides, and inorganic hydroxides.
• the above-mentioned inorganic particles may be composed of one kind of these materials, or may contain two or more kinds.
• the material constituting the inorganic particles is preferably silica, boron nitride, alumina, titania, or zirconia, more preferably silica or alumina, and particularly preferably silica.
• the silica may be crystalline silica or amorphous silica, but amorphous silica is preferred.
• the content of the inorganic particles is not particularly limited, but for example, from the viewpoint of easily obtaining a cured product with improved mechanical strength, the content of the inorganic particles is determined by the amino groups in the composition of the present disclosure.
• the content is preferably 5 to 100 parts by weight based on 100 parts by weight of the total content of the polysiloxane (A) and the polymer (B). More preferably it is 15 parts by mass or more, and even more preferably 25 parts by mass or more.
• the upper limit is more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. That is, the content of the inorganic particles is more preferably 15 to 60 parts by mass, and even more preferably is 25 to 50 parts by mass.
• compositions of the present disclosure may also contain antioxidants.
• the antioxidant is not particularly limited, and conventionally known antioxidants can be used, such as phenolic antioxidants, thioether antioxidants, phosphite antioxidants, and the like. In order to more effectively exhibit antioxidant performance, it is preferable to use a phenolic antioxidant and a thioether antioxidant in combination.
• the content of the antioxidant is equal to the total content of the amino group-containing polysiloxane (A) and the polymer (B) in the composition of the present disclosure.
• the amount is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight.
• the composition of the present disclosure may contain a thickener to improve processability and stability.
• a thickener high viscosity polymers or clays that are soluble or dispersed in organic solvents can be used, such as polyester thickeners, polyamide thickeners, polyimide thickeners, polyamic acids (polyamic acid Examples include acid)-based thickeners, montmorillonite clay-based thickeners, and the like.
• polyimide thickeners and polyamic acid thickeners are preferred from the viewpoint of maintaining or reducing the heat resistance and dielectric constant of the cured product after heating.
• the content of the thickener is equal to the total content of the amino group-containing polysiloxane (A) and the polymer (B) in the composition of the present disclosure.
• the amount is preferably 1 to 40 parts by weight, more preferably 2.5 to 35 parts by weight, and still more preferably 5 to 30 parts by weight.
• composition of the present disclosure may contain additives such as a curing accelerator within a range that does not impair the effects of the present invention.
• the method for preparing the composition of the present disclosure is not particularly limited, and the composition can be prepared by mixing each component using a conventionally known method.
• the composition of the present disclosure can be obtained by mixing the amino group-containing polysiloxane (A) and the polymer (B) in a predetermined ratio, but when the amino group-containing polysiloxane is liquid; may be used for mixing as is, or may be used for mixing in the form of a solution dissolved in the above-mentioned preferred solvent.
• the amino group-containing polysiloxane is a solid, it is preferably mixed in the form of a solution dissolved in the above-mentioned preferred solvent.
• the above-mentioned mixing method is not particularly limited, and conventionally known mixing methods such as stirring may be employed.
• the inorganic particles are mixed in the mixture of the above amino group-containing polysiloxane (A) and the above polymer (B) in the form of a dispersion dispersed in a solvent. It is preferable to do so.
• the solvent for dispersing the inorganic particles it is preferable to use the above-mentioned preferred solvents.
• the dispersion method is not particularly limited, and for example, conventionally known methods such as a melt kneading method, a method using a mixer, a ball mill, a jet mill, a disper, a sand mill, a roll mill, a pot mill, a paint shaker, etc. Examples include mixing and dispersing methods. A dispersant or the like may be added as appropriate.
• the composition of the present disclosure contains additives such as an antioxidant and a curing accelerator, these additives are added directly or as a solution dissolved in a solvent to the amino group-containing polysiloxane (A) and the polymer. What is necessary is just to mix it at the time of mixing with union (B), or after mixing it.
• compositions of the present disclosure can be prepared by the methods described above.
• a defoaming treatment By performing the defoaming treatment, it is possible to suppress the incorporation of air bubbles into a cured product obtained by curing the composition of the present disclosure.
• the composition of the present disclosure is preferably used as a curable composition.
• the cured product of the present disclosure is a cured product obtained by curing the composition of the present disclosure described above.
• the method for producing a cured product of the present disclosure is not particularly limited as long as it is a method of producing a cured product by curing the composition of the present disclosure, but it preferably includes the following steps 1 and 2 in this order. .
• Step 1 Coating step of applying the composition of the present disclosure to a substrate
• Step 2 Curing step of curing the applied composition
• the method of coating the base material in step 1 is not particularly limited.
• methods such as a spin coating method, a slit coating method, a spray method, a roll coating method, an inkjet method, a screen printing method, a gravure printing method, a flexo printing method, a dipping method, etc. can be used.
• the thickness of the coating film is not particularly limited, but is preferably 10 to 250 ⁇ m. More preferably, it is 20 ⁇ m or more, and still more preferably 30 ⁇ m or more.
• the upper limit is more preferably 200 ⁇ m or less, still more preferably 150 ⁇ m or less. That is, the thickness of the coating film is more preferably 20 to 200 ⁇ m, and even more preferably 30 to 150 ⁇ m. It is preferable to adjust the thickness of the coating film so that it becomes a preferable film thickness as a cured product, which will be described later.
• Examples of the base material include metal base materials, silicon/inorganic base materials, and composite materials.
• Examples of the metal base material include base materials whose surface is mainly composed of metal such as aluminum, copper, gold, silver, titanium, and molybdenum.
• Examples of the above-mentioned silicon/inorganic base material include base materials whose main components are silicon-related materials such as silicon, silicon nitride, and silicon oxide, and inorganic materials such as glass and quartz.
• Examples of the above-mentioned composite base material include a base material made of resin, silicon, silicon nitride, silicon oxide, glass, quartz, etc., and a thin metal film or the like is provided on a part or all of the surface of the base material.
• the shape of the base material is not particularly limited.
• a plate shape, a linear shape, etc. are preferable.
• base materials silicon/inorganic base materials and metal base materials are preferred, and metal base materials are more preferred, from the viewpoint that a cured product with excellent adhesion to the cured product of the present disclosure tends to be obtained.
• the curing method in step 2 is preferably a heating method.
• the heating temperature can be appropriately selected depending on the type of substrate, heating time, etc., but is usually preferably in the range of 100 to 400°C, more preferably in the range of 150 to 350°C.
• the heating time can be appropriately selected depending on the type of substrate, heating temperature, etc., but is usually preferably 1 minute to 10 hours, more preferably 10 minutes or more, and even more preferably 30 minutes or more. The upper limit is more preferably 5 hours or less. Heating may also be carried out by continuously increasing the temperature at a predetermined rate and maintaining the temperature at a predetermined temperature. For example, the first heating may be performed at a temperature of 100°C or more and less than 200°C for a predetermined period of time.
• the heating temperature is increased stepwise, such as performing second heating at a temperature of 200°C or more and less than 300°C for a predetermined time, and then performing third heating at a temperature of 300°C or more and less than 400°C for a predetermined time.
• the atmosphere for heating is not particularly limited, but it is preferable to conduct the heating in an inert atmosphere such as a nitrogen gas atmosphere or an oxidizing atmosphere such as air.
• step 2 is performed after the step 1, a method of performing the step 2 simultaneously with the step 1 can also be adopted. This method is achieved, for example, by applying the coating while heating the base material in step 1.
• Step 3 Solvent removal step in which part or all of the solvent is removed from the applied composition
• the solvent may be removed by heating, reducing pressure (degassing), or a combination thereof.
• a method is preferably adopted. Therefore, in the solvent removal step, part or all of the solvent is distilled off from the film of the composition applied to the base material by heating and/or reduced pressure (degassing).
• the heating temperature in the solvent removal step is preferably 50 to 150°C, more preferably 120°C or less, and even more preferably less than 100°C.
• the heating time is preferably 30 seconds to 2 hours, more preferably 10 minutes to 1 hour.
• the above step 3 is preferably carried out after the above step 1, but it can also be carried out simultaneously with the above step 1. Moreover, although it is preferable that the above step 3 is performed before the above step 2, it can also be performed simultaneously with the above step 2.
• a preferred method is to perform Step 1 above, then heat the substrate and the composition applied to the substrate, and then perform Steps 2 and 3 continuously. As described above, a cured product obtained by curing the composition of the present disclosure is formed on the surface and/or inside of various substrates.
• the thickness of the cured product is not particularly limited, but is preferably 5 to 500 ⁇ m. More preferably, it is 10 ⁇ m or more, and still more preferably 15 ⁇ m or more.
• the upper limit is more preferably 400 ⁇ m or less, still more preferably 300 ⁇ m or less. That is, the film thickness of the cured product is more preferably 10 to 400 ⁇ m, and even more preferably 15 to 300 ⁇ m.
• the above film thickness can be measured using a micrometer.
• the dielectric constant of the cured product is not particularly limited, but the dielectric constant at 10 GHz is preferably 2.0 or more and 2.9 or less. It is more preferably 2.7 or less, still more preferably 2.6 or less, particularly preferably 2.5 or less.
• the lower limit is more preferably 2.1 or more. That is, the dielectric constant of the cured product at 10 GHz is more preferably 2.1 to 2.7, still more preferably 2.1 to 2.6, particularly preferably 2.1 to 2.5. be.
• the above dielectric constant can be measured by the cavity resonator perturbation method using network analyzer E8361A (manufactured by Agilent Technologies) under the conditions of temperature 25 ° C., humidity 50%, and frequency 10 GHz. It is preferable to adopt the value.
• the cured product has excellent heat resistance.
• the temperature at which weight loss begins is high.
• the temperature at which the weight loss is 5% by mass when the temperature of the cured product is raised from room temperature at a heating rate of 10° C./min in an air atmosphere is referred to as the 5% weight loss temperature.
• the 5% weight loss temperature of the cured product is preferably 340°C or higher.
• the temperature is more preferably 360°C or higher, and still more preferably 380°C or higher.
• the upper limit is not particularly limited, it is usually 450°C or lower.
• the 5% weight loss temperature of the cured product is preferably 340 to 450°C, more preferably 360 to 450°C, and still more preferably 380 to 450°C.
• the above 5% weight loss temperature can be measured using a TG-DTA device, and it is preferable to use the value obtained by this method.
• TG-DTA device As the TG-DTA device, TG-DTA2000SR (manufactured by NESZTCH) and MTC1000SA (manufactured by Bruker) are recommended.
• the elongation of the cured product is not particularly limited, but is preferably 5 to 100%. It is more preferably 10% or more, still more preferably 20% or more, even more preferably 30% or more, and particularly preferably 40% or more.
• the upper limit is more preferably 150% or less. That is, the elongation of the cured product is more preferably 10 to 150%, still more preferably 20 to 150%, even more preferably 30 to 150%, particularly preferably 40 to 150%.
• the above-mentioned elongation means the elongation at break when a tensile test is performed, and can be measured by the method described below, and it is preferable to employ the value obtained by this method.
• the cured product is preferably an insulating film.
• Preferred aspects of the insulating film such as film thickness, dielectric constant, elongation, and 5% weight loss temperature, are the same as the respective preferred aspects of the cured product.
• composition of the present disclosure a cured product obtained by curing the composition, and an insulating film is not particularly limited, and can be used for various purposes.
• the composition of the present disclosure is preferably used to form an insulating film for electrical/electronic devices, such as electronic equipment such as computers, communication equipment such as mobile phones, network-related electronic equipment such as servers, etc. .
• electrical/electronic devices such as electronic equipment such as computers, communication equipment such as mobile phones, network-related electronic equipment such as servers, etc.
• insulated wires used in electrical equipment with high applied voltages such as motors used at high voltages, are required to improve the corona discharge starting voltage, and reducing the dielectric constant of the insulating layer in insulated wires is effective. It is said that Therefore, the composition of the present disclosure can be suitably used to form an insulating layer of an insulated wire that constitutes an electric coil included in the motor.
• Step 1A 16,500 g of methanol, 3,200 g of water, 1,300 g of 25% aqueous ammonia, and 110 g of acetone were added to a 50 L SUS container equipped with a stirrer, a dripping port, and a thermometer, and stirred for 30 minutes to obtain a uniform mixed solution.
• the temperature of the above mixed solution was adjusted to 49 to 51° C., and while stirring, 5700 g of tetramethyl orthosilicate (TMOS) was added dropwise from the dropping port over 90 minutes. After the dropwise addition was completed, stirring was continued for 30 minutes while maintaining the above liquid temperature to obtain an alcoholic solution suspension of silica particles (suspension 1A).
• TMOS tetramethyl orthosilicate
• Step 1C Using a commercially available ultrafiltration membrane equipped with a ceramic tubular ultrafiltration membrane with a molecular weight cutoff of about 10,000, the suspension 1B obtained in step 1B was subjected to solvent replacement at room temperature while adding methanol as appropriate. By concentrating the mixture until the SiO 2 concentration reached approximately 11%, a methanol suspension (suspension 1C) of silica particles having methacrylic groups on the particle surface was obtained.
• Step 1E By weighing 1800 g of the suspension 1D obtained in the step 1D and concentrating the solvent by vacuum distillation at 40 ° C. with a rotary evaporator at a reduced pressure of 30 to 300 hPa, propylene glycol monomethyl ether (PGM) was successively added. By replacing the solvent of the suspension with PGM and concentrating the suspension so that the SiO 2 concentration was approximately 50%, a PGM dispersion (dispersion 1) of silica particles having methacrylic groups on the particle surface was obtained. The average particle diameter of the silica particles in the dispersion was 24 nm.
• the average particle diameter is determined by measuring the diameter of 50 arbitrary particles from the SEM image taken with a scanning electron microscope JSM-7600F manufactured by JEOL with a caliper, and calculating the arithmetic mean value of the 50 diameters. Adopted. In addition, when taking photographs with a scanning electron microscope, the measurement magnification was set so that 50 to 100 particles were found in the field of view of one photograph.
• Example 1 In a vial, as the amino group-containing polysiloxane (A), 3.44 g of KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 2200 g/mol), which is an amino-modified silicone, and as the polymer (B), styrene/ 1.00 g of a solution of Alastar 700 (manufactured by Arakawa Chemical Industries, Ltd., carboxyl group equivalent: 175-200 g/mol), which is a maleic acid half ester copolymer, dissolved in propylene glycol monopropyl ether to a concentration of 50% by mass.
• Alastar 700 manufactured by Arakawa Chemical Industries, Ltd., carboxyl group equivalent: 175-200 g/mol
• the resulting composition (1) was applied to a flat PTFE plate with a constant thickness and heated at 100°C for 30 minutes, 200°C for 30 minutes, 250°C for 30 minutes, and 300°C for 1 hour.
• a cured film (1) with a thickness of 100 to 150 ⁇ m was formed on a PTFE plate by heat curing, and an independent film of the cured film (1) was obtained by peeling off the PTFE plate.
• the dielectric constant and other properties of the cured film (1) were evaluated. The results are shown in Table 2.
• Example 2 was carried out in the same manner as in Example 1, except that the types and amounts of each component such as the amino group-containing polysiloxane (A) and the polymer (B) in Example 1 were changed as shown in Table 1. -7 compositions were prepared, respectively. Using each of the obtained compositions, cured films (2) to (7) were obtained in the same manner as in Example 1. On the other hand, in the compositions of Comparative Examples 1 and 2, phase separation and gelation occurred, making it impossible to obtain a uniform composition and making it impossible to form a cured product film. The dielectric constant, 5% weight loss temperature, and elongation of each cured film obtained in each of these Examples were evaluated. The results are shown in Table 2.
• - Alastair 700 manufactured by Arakawa Chemical Industry Co., Ltd., styrene-maleic acid resin half ester, acid value 175-200.
• ⁇ ADEKA STAB AO-30 Manufactured by ADEKA, phenolic antioxidant, - ADEKA STAB AO-503: manufactured by ADEKA, thioether antioxidant Also, the value (100) of the total (parts by mass) in Table 1 is the value rounded to the first decimal place.
• Thickener synthesis example 1 2.5 g of XIRAN 3500 (manufactured by POLYSCOPE, styrene-maleic anhydride copolymer) and 2.5 g of butyl acetate were placed in a vial and dissolved while heating at 60° C. with stirring. A solution prepared by dissolving 0.8 g of 2-ethylhexylamine in 0.8 g of butyl acetate and 2.0 g of propylene glycol monopropyl ether was added dropwise to the obtained solution to obtain a thickener (1).
• Example 8 4 parts by mass of the thickener (1) obtained above was added to 100 parts by mass of the composition (1) obtained in Example 1, and the mixture was stirred to obtain a composition (8).
• the viscosity of the obtained composition (8) and composition (1) was measured at 25°C using an E-type viscometer (TPE-100, manufactured by Toki Sangyo Co., Ltd.), and the viscosity was 1010 mPa ⁇ s and 300 mPa, respectively. ⁇ It was s.
• the resulting composition (8) was applied to a flat PTFE plate with a constant thickness and heated at 100°C for 30 minutes, 200°C for 30 minutes, 250°C for 30 minutes, and 300°C for 1 hour.
• a cured film (8) having a thickness of 150 ⁇ m was formed on a PTFE plate by heat curing, and an independent film of the cured film (8) was obtained by peeling off the PTFE plate.
• the dielectric constant of the cured film (8) was 2.69, and the 5% weight loss temperature was 380°C.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Insulating Materials (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=89706212

Family Applications (1)

Country Status (3)

Citations (4)

Family Cites Families (2)

• 2023
  • 2023-06-16 JP JP2024536844A patent/JPWO2024024320A1/ja active Pending
  • 2023-06-16 WO PCT/JP2023/022343 patent/WO2024024320A1/ja not_active Ceased
  • 2023-06-20 TW TW112123160A patent/TW202409730A/zh unknown

Patent Citations (4)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events