Reinforced silicone resin films

(Cross-reference of related applications) None.

The present invention relates to a reinforced silicone resin film, more specifically, a reinforced silicone resin film containing at least two polymer layers, wherein at least one of the polymer layers has an average of at least two silicons per molecule. With respect to a reinforced silicone resin film containing a cured product of at least one silicone resin having a hydrogen atom, a hydroxy group or a hydrolyzable group bonded to the polymer layer, and at least one of the polymer layers containing a carbon nanomaterial.

Silicone resins are useful in a variety of applications due to their unique combination of properties, including high thermal stability, good moisture resistance, excellent flexibility, high oxidation resistance, low dielectric constant and high transparency. is there. For example, silicone resins are widely used as protective or dielectric coatings in the automotive, electronic, architectural, electrical and aerospace industries.

<p> While silicone resin coatings can be used to protect, insulate or bond various substrates, free-standing silicone resin films have low tear strength, high brittleness, low glass transition temperature and high heat. It has limited usefulness due to its coefficient of expansion. Therefore, there is a need for self-supporting silicone resin films with improved mechanical and thermal properties.</p>

<p> The present invention With the first polymer layer, With the second polymer layer on the first polymer layer Essentially from, at least one of these polymer layers produces a cured product of at least one silicone resin having an average of at least two silicon-bonded hydrogen atoms, hydroxy or hydrolyzable groups per molecule. If both of the above polymer layers contain a cured product of a silicone resin, then both of the polymer layers are (i) carbon nanomaterials. Reinforced silicone resin films comprising (ii) fiber reinforcing materials and reinforcing materials selected from mixtures containing (iii) (i) and (ii).</p><p> The present invention is also a reinforced silicone resin film. With the first polymer layer, With the second polymer layer on this first polymer layer, With at least one additional polymer layer on this second polymer layer And at least one of these polymer layers contains a cured product of at least one silicone resin having an average of at least two silicon-bonded hydrogen atoms, hydroxy or hydrolyzable groups per molecule, and At least one of these polymer layers relates to a reinforced silicone resin film containing carbon nanomaterials.</p><p> The reinforced silicone resin film of the present invention has a low coefficient of thermal expansion and high resistance to thermally induced cracks.</p><p> The reinforced silicone resin film of the present invention is useful for applications that require a film with high thermal stability, flexibility, mechanical strength and transparency. For example, this silicone resin film can be used as an integral element of flexible displays, solar cells, flexible electronic circuit boards, touch screens, fire resistant wallpaper and impact resistant windows. This film is also a suitable substrate for transparent or opaque electrodes.</p>

<figref num="1">FIG. 1A is a plan view (that is, top view) of the reinforced silicone resin film of Example 3 before the heat treatment. FIG. 1B is a cross-sectional micrograph of the reinforced silicone resin film of Example 3 before the heat treatment. FIG. 1C is a plan view micrograph of the reinforced silicone resin film of Example 3 after the heat treatment.</figref><figref num="2">2A and 2B are plan view micrographs of the non-reinforced silicone resin film of Comparative Example 1 before and after the heat treatment, respectively.</figref><figref num="3">It is a plan view micrograph of the reinforced silicone resin film of Example 4 after the heat treatment.</figref><figref num="4">It is a plan view micrograph of the reinforced silicone resin film of Example 5 after the heat treatment.</figref>

Only in the drawings, the symbol um represents micron.

As used herein, the term "group R in silicone resin"²... mol% is a hydrogen, hydroxy, or hydroslysable group "is the group R in the silicone resin.²Is defined as 100 times the ratio of the number of moles of hydrogen, hydroxy, or hydroslysable groups bonded to silicon in the resin to the total number of moles of. In addition, the term "group R in silicone resin"⁴... mol% is a hydroxy or hydroslysable group "is the group R in the silicone resin.⁴It is defined as 100 times the ratio of the number of moles of hydroxy or hydrolysable groups in the resin to the total number of moles of.

The first reinforced silicone resin film according to the present invention is With the first polymer layer, With a second polymer layer on this first polymer layer Essentially from, at least one of the polymer layers contains a cured product of at least one silicone resin having an average of at least two silicon-bonded hydrogen atoms, hydroxy or hydrolyzable groups per molecule. , And at least one of the polymer layers contains a carbon nanomaterial, but if both of the polymer layers contain a cured product of a silicone resin, then both of the polymer layers are (i) carbon nanomaterials. Includes (ii) fiber reinforcements and reinforcements selected from mixtures containing (iii) (i) and (ii).

The first polymer layer of the first reinforced silicone resin film typically has a thickness of 0.01 to 1000 μm, or 5 to 500 μm, or 10 to 100 μm.

The first polymer layer of the first reinforced silicone resin film can include a thermoplastic polymer or a thermosetting polymer. The thermoplastic or thermosetting polymer may be a homopolymer or a copolymer. Further, the thermoplastic polymer or thermosetting polymer may be a silicone polymer or an organic polymer. As used herein and below, the term "thermoplastic polymer" has the property of changing to a fluid (fluid) state when heated and rigid (non-fluid) when cooled. Refers to a polymer. Also, the term "thermosetting polymer" refers to a cured (ie, crosslinked) polymer that does not change to a fluid state upon heating.

Examples of thermoplastic polymers include thermoplastic silicone polymers (eg poly (diphenylsiloxane-co-phenylmethylsiloxane)) and thermoplastic organic polymers (eg polyolefins, polysulfones, polyacrylates and polyetherimides). Not limited to.

Examples of thermosetting polymers include thermosetting silicone polymers (eg, cured silicone elastomers, silicone gels and cured silicone resins), and thermosetting organic polymers (eg, epoxy resins, cured amino resins, cured polyurethanes, etc. Examples include, but are not limited to, cured polyimides, cured phenolic resins, cured cyanate resins, cured bismaleimide resins, cured polyesters and cured acrylic resins.

In addition to the thermoplastic or thermosetting polymer, the first polymer layer of the first reinforced silicone resin film contains a reinforced material selected from carbon nanomaterials, fiber reinforced materials and mixtures thereof, respectively, as described below. Can include.

The second polymer layer of the first reinforced silicone resin film is as described and illustrated above for the first polymer layer. The first and second polymer layers of this first reinforced silicone resin film have many physical and chemical properties, including thickness, polymer composition, crosslink density and concentration of carbon nanomaterials or other reinforced materials. At least one is different.

At least one of the polymer layers of the first reinforced silicone resin film is a cured product of at least one silicone resin having an average of at least two silicon-bonded hydrogen atoms, hydroxy groups or hydrolyzable groups per molecule. including. As used herein, the term "cured product of at least one silicone resin" refers to a crosslinked product of at least one silicone resin that has a three-dimensional network structure. The silicone resin, the method for preparing the resin, and the method for preparing the cured product of the silicone resin are described later in the method for preparing the first reinforced silicone resin film of the present invention.

At least one of the polymer layers of the first reinforced silicone resin film contains carbon nanomaterials. The carbon nanomaterial may be any carbon material having at least one physical dimension (eg particle size, fiber diameter, layer thickness) less than about 200 nm. Examples of carbon nanomaterials are carbon nanoparticles with three dimensions less than 200 nm (eg quantum dots, hollow spheres and fullerenes), and fibrous carbon nanomaterials with two dimensions less than about 200 nm (eg nanotubes (eg nanotubes). Single-walled nanotubes and multi-walled nanotubes) and nanoparticles (eg, axially aligned platelets, herringbone or fishbone nanofibers), and one dimension less than about 200 nm. Examples include, but are not limited to, carbon nanomaterials in layers (eg, carbon nanoplatelets (eg, expanded graphite and graphene sheets)). The carbon nanomaterial may be conductive or semi-conductive.

The carbon nanomaterial may be an oxidized carbon nanomaterial prepared by treating the above-mentioned carbon nanomaterial with an oxidizing acid or a mixture of acids at a high temperature. For example, carbon nanomaterials can be obtained by heating the material in a mixture of concentrated nitric acid and concentrated sulfuric acid (1: 3 volume / volume, 25 mL per gram of carbon) at a temperature of 40-150 ° C for 1-3 hours. , Can be oxidized.

The carbon nanomaterial may be a single carbon nanomaterial or a mixture containing at least two different carbon nanomaterials (each as described above).

The concentration of carbon nanomaterial in the first and / or second polymer layer is typically 0.0001 to 99% (weight / weight) or 0.001 to 50% (weight / weight) based on the total weight of the polymer layer. Weight / weight), or 0.01 to 25% (weight / weight), or 0.1 to 10% (weight / weight), or 1 to 5% (weight / weight).

Methods of preparing carbon nanomaterials are well known in the art. For example, carbon nanoparticles (eg, fullerenes) and fibrous carbon nanomaterials (eg, nanotubes and nanofibers) can be prepared using at least one of the following methods: arc discharge, laser ablation. And catalytic chemical vapor deposition. In the arc discharge process, the arc discharge between the two graphite rods produces single-walled nanotubes, multi-walled nanotubes and fullerenes, depending on the gas atmosphere. In the laser ablation method, the graphite target carrying the metal catalyst is irradiated by a laser in a tube furnace to produce single-walled and multi-walled nanotubes. In catalytic chemical vapor deposition, a carbon-containing gas or gas mixture is introduced into a tube furnace containing a metal catalyst at a temperature of 500-1000 ° C (and at various pressures) to produce carbon nanotubes and nanofibers. To do. Carbon nanoplatelets can be prepared by intercalation and exfoliation of graphite.

If both of the polymer layers of the first reinforced silicone resin film contain a cured product of the silicone resin, both of the polymer layers are (i) carbon nanomaterials, (ii) fiber reinforced materials, and (iii) (i). ) And (ii) containing a reinforcing material selected from the mixture. The carbon nanomaterials are as described and illustrated above. The polymer layer can contain the same or different reinforcements selected from (i), (ii) and (iii), respectively.

The fiber reinforcing material may be any reinforcing material containing fibers as long as the reinforcing material has a high elastic modulus and a high tensile strength. Fiber reinforcements typically have a Young's modulus of at least 3 GPa at 25 ° C. For example, this reinforcement typically has a Young's modulus of 3 to 1,000 GPa, or 3 to 200 GPa, or 10 to 100 GPa at 25 ° C. In addition, the reinforcement typically has a tensile strength of at least 50 MPa at 25 ° C. For example, this reinforcement typically has a tensile strength at 25 ° C of 50-10,000 MPa, or 50-1,000 MPa, or 50-500 MPa.

The fiber reinforcement may be a woven fabric (eg cloth), a non-woven fabric (eg matte or roving), or unbundled (individual) fibers. Reinforcing fiber is typically cylindrical and has a diameter of 1-100 μm, or 1-20 μm, or 1-10 μm. The unbundled fibers may be continuous (this means that the fibers extend over the entire reinforced silicone resin film in a manner that is almost unbreakable) or may be chopped.

Fiber reinforcements are typically heat treated prior to use to remove organic contaminants. For example, fiber reinforced plastics are typically heated in air at high temperatures (eg 575 ° C) for a suitable period of time (eg 2 hours).

Examples of fiber reinforcements include glass fibers, quartz fibers, graphite fibers, nylon fibers, polyester fibers, aramid fibers (eg, Kevlar® and Nomex®, polyethylene fibers, polypropylene fibers, and silicon carbide fibers. Reinforcement materials including, but are not limited to these.

The concentration of fiber reinforced material in the first and / or second polymer layer is typically 0.1-95% (weight / weight), or 5-75% (weight / weight), based on the total weight of the polymer layer. Weight / weight), or 10-40% (weight / weight).

When one or both of the polymer layers of the first reinforced silicone resin film contain a mixture of carbon nanomaterials and fiber reinforced materials, the concentration of the mixture is typically 0.1-96% based on the total weight of the polymer layers. (Weight / weight), or 5 to 75% (weight / weight), or 10 to 40% (weight / weight).

The first polymer layer and the second polymer layer can be prepared as described later in the method for preparing the first reinforced silicone resin film of the present invention.

The first reinforced silicone resin film is The process of forming the first polymer layer on the release liner, With the step of forming a second polymer layer on top of this first polymer layer At least one of the polymer layers comprises a cured product of at least one silicone resin having a hydrogen atom, a hydroxy group or a hydrolyzable group bonded to at least two silicons on average per molecule. If both of these polymer layers contain a cured product of a silicone resin, and at least one of the polymer layers contains a carbon nanomaterial, then both of the polymer layers are (i) carbon nanomaterials. , (Ii) can be prepared by a method comprising a fiber reinforcing material and a reinforcing material selected from a mixture containing (iii) (i) and (ii).

In the first step of the method of preparing the first reinforced silicone resin film, the first polymer layer is formed on the release liner.

The release liner may be any rigid or flexible material with a surface that allows the first polymer layer to be removed without damage. Examples of release liners include silicon, quartz, fused quartz, aluminum oxide, ceramics, glass, metal foils, polyolefins (eg polyethylene, polypropylene, polystyrene and polyethylene terephthalates), fluorocarbon polymers (eg polytetrafluoroethylene and polyvinyl fluoride). , Polyamide (eg, nylon), polyimide, polyester (eg, polymethyl methacrylate), epoxy resin, polyether, polycarbonate, polysulfone, and polyethersulfone, but are not limited thereto. The release liner may be the material cited above, having a surface treated with a release agent (eg, a silicone release agent).

The first polymer layer can be formed using various methods, depending on the composition of the polymer layer. For example, if the first polymer layer contains a thermoplastic polymer, the layer is (i) coated with a composition containing the thermoplastic polymer in a fluid state, and (ii) the heat of the coated release liner. It can be formed by converting the thermoplastic polymer into a solid state.

In step (i) of the method of forming the first polymer layer described above, the release liner is coated with a composition containing a fluidized thermoplastic polymer.

The composition containing the thermoplastic polymer may be any composition containing the thermoplastic polymer in a fluid (ie, liquid) state. As used herein, the term "fluid thermoplastic polymer" means that the polymer is in a molten state or is dissolved in an organic solvent. For example, the composition is the melting point of the polymer (T_m) Or glass transition temperature (T_g) May contain a molten thermoplastic polymer, or the composition may contain a thermoplastic polymer and an organic solvent.

The thermoplastic polymer of the composition is as described and exemplified above for the first reinforced silicone resin film. The thermoplastic polymer may be a single thermoplastic polymer or a mixture (ie, a blend) containing two or more different thermoplastic polymers. For example, the thermoplastic polymer may be a polyolefin blend.

The organic solvent may be any protic, aprotic, or bipolar aprotic organic solvent that does not react with the thermoplastic polymer and is miscible with the polymer. Examples of organic solvents include saturated aliphatic hydrocarbons (eg n-pentane, hexane, n-heptane, isooctane and dodecane), alicyclic hydrocarbons (eg cyclopentane and cyclohexane), aromatic hydrocarbons (eg benzene, etc.). Toluene, xylene and mesitylene), cyclic ethers (eg tetrahydrofuran (THF) and dioxane), ketones (eg methylisobutylketone (MIBK)), halogenated alcohols (eg trichloroethane), halogenated aromatic hydrocarbons (eg bromobenzene and chlorobenzene) ), As well as alcohols (eg methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 1,1-dimethyl-1-ethanol, pentanol, hydrocarbons, cyclos. (Hexanol, heptanol and octanol), but not limited to these.

The organic solvent may be a single organic solvent or a mixture containing two or more different organic solvents, each of which is described and exemplified above.

Compositions comprising thermoplastic polymers can further comprise the carbon nanomaterials described and exemplified above.

The release liner may be coated with a composition comprising a fluidized thermoplastic polymer using conventional coating techniques such as spin coating, dipping, spraying, brushing, extrusion or screen printing. The amount of composition is sufficient to form a first polymer layer with a thickness of 0.01-1000 μm.

In step (ii) of the method described above, the thermoplastic polymer of the coated release liner is converted to a solid state. If the composition used to coat the release liner contains a molten thermoplastic polymer, the thermoplastic polymer will have a liquid-solid transition temperature (T)._gOr T_m) It can be converted to a solid state by allowing the polymer to cool to a lower temperature, eg room temperature. If the composition used to coat the release liner comprises a thermoplastic polymer and an organic solvent, the thermoplastic polymer can be converted to a solid state by removing at least a portion of the solvent. The organic solvent can be removed by vaporizing the solvent at room temperature or by heating the coating to a moderate temperature, for example below the solid-liquid transition temperature of the polymer.

The method of forming the first polymer layer containing the thermoplastic polymer is to apply a second release liner to the coated release liner of the first step after step (i) and before step (ii). The steps of forming the assembly and compressing the assembly can be further included. The assembly can be compressed to remove excess composition and / or invading air and reduce the thickness of the coating. The assembly can be compressed using conventional equipment (eg stainless steel rollers, hydraulic presses, rubber rollers or laminated roll sets). The assembly is typically compressed at a pressure of 1,000 Pa-10 MPa and at a temperature of room temperature (about 23 ± 2 ° C) to 200 ° C.

If the same composition is used in each coating step, the method of forming the first polymer layer containing the thermoplastic polymer is a step of repeating steps (i) and (ii) to further increase the thickness of the polymer layer. Can include.

If the first polymer layer contains a thermosetting (ie, crosslinked) polymer, the layer will (i) coat the release liner with a curable composition containing the thermosetting polymer and (ii) coat the release liner. It can be formed by curing the thermosetting polymer of.

In step (i) of the method immediately prior to forming the first polymer layer, the release liner is coated with a curable composition comprising a thermosetting polymer.

The curable composition containing a thermosetting polymer may be any curable composition containing a thermosetting polymer. As used herein and below, the term "thermosetting polymer" refers to a polymer that has the property of being persistently rigid (immobilized) when cured (ie, crosslinked). The curable composition typically comprises a thermosetting polymer and additional components such as an organic solvent, a cross-linking agent and / or a catalyst.

Examples of curable compositions containing thermosetting polymers include curable silicone compositions (eg, hydrosilylated curable silicone compositions, condensation curable silicone compositions and peroxide curable silicone compositions), curable silicones. Compositions (eg, silicone and silicone compositions), curable polyamide compositions, curable epoxy resin compositions, curable amino resin compositions, curable polyurethane compositions, curable polyimide compositions, curable polyester compositions, and Curable acrylic resin compositions include, but are not limited to.

A curable composition comprising a thermosetting polymer may also be a condensation curable silicone composition comprising a silicone resin having a hydrogen atom, a hydroxy group or a hydrolyzable group bonded to at least two silicons on average per molecule. Good.

The condensation-curable silicone composition may be any condensation-curable silicone composition containing a silicone resin having a hydrogen atom, a hydroxy group or a hydrolyzable group bonded to at least two silicons on average per molecule. Typically, the condensation-curable silicone composition comprises the silicone resin described above, and optionally a cross-linking agent and / or a condensation catalyst having a hydrolyzable group attached to silicon.

Silicone resins in condensation-curable silicone compositions are typically copolymers containing T units, T and Q siloxane units or T and / or Q siloxane units in combination with M and / or D siloxane units. is there. Further, this silicone resin may be a silicone resin modified with rubber, which will be described later in the second embodiment of the condensation curable silicone composition.

According to the first embodiment, the condensation curable silicone composition has the formula (R).¹R²₂SiO_1/2)_w(R²₂SiO_2/2)_x(R²SiO_3/2)_y(SiO_4/2)_zContains silicone resin having (I) (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyl and R²Is R¹, -H, -OH, or a hydrolyzable group, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, z is 0 to 0.95, w + x + y + z = 1, y + z is 0.05 to 1, and w + x is 0 to 0.95, but this silicone resin averages at least two hydrogens bound to silicon per molecule. Has an atom, a hydroxy group or a hydrolyzable group).

R¹The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by are typically having 1 to 10 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Acyclic hydrocarbyls containing at least 3 carbon atoms and halogen-substituted hydrocarbyl groups can have a branched or non-branched structure. R¹Examples of hydrocarbyl groups represented by are alkyl (eg, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-Ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl and decyl), cycloalkyl (eg cyclopentyl, cyclohexyl and methylcyclohexyl), Aryl (eg phenyl and naphthyl), Alkalur (eg trill and xsilyl), Aralkyl (eg benzyl and phenethyl), Alkenyl (eg vinyl, allyl and propenyl), arylalkenyl (eg styryl and cinnamyl), and alkynyl (eg ethynyl and synamyl). Propinyl), but is not limited to these. R¹Examples of halogen-substituted hydrocarbyl groups represented by are 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2,3, Examples include, but are not limited to, 3-tetrafluoropropyl and 2,2,3,3,4,4,5,5-octafluoropentyl.

As used herein, the term "hydrolyzable group" is used in the presence or absence of a catalyst at any temperature from room temperature (about 23 ± 2 ° C) to 100 ° C where the group bonded to silicon is at room temperature (about 23 ± 2 ° C) to 100 ° C. It means that it reacts with water within a few minutes (for example, 30 minutes) to form a silanol (Si-OH) group. R²Examples of hydrolyzable groups represented by are -Cl, -Br, -OR.³, -OCH₂CH₂OR³, CH₃C (= O) O-, Et (Me) C = NO-, CH₃C (= O) N (CH₃)-, And -ONH₂(In the formula, R³Is C₁~ C₈Hydrocarbyl, or C₁~ C₈Halogen-substituted hydrocarbyl), but is not limited to these.

R³The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by are typically having 1 to 8 carbon atoms, or 3 to 6 carbon atoms. Acyclic hydrocarbyls containing at least 3 carbon atoms and halogen-substituted hydrocarbyl groups can have a branched or non-branched structure. R³Examples of hydrocarbyl groups represented by are non-branched and branched alkyls (eg, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1- Dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl and octyl), cycloalkyl (eg cyclopentyl, cyclohexyl) And methylcyclohexyl), phenyl, alkalinel (eg trill and xylyl), aralkyl (eg benzyl and phenethyl), alkenyl (eg vinyl, allyl and propenyl), arylalkenyl (eg styryl), and alkynyl (eg ethynyl and propynyl) However, it is not limited to these. R³Examples of halogen-substituted hydrocarbyl groups represented by are, but are not limited to, 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl and dichlorophenyl.

In the silicone resin formula (I), the subscripts w, x, y and z are mole fractions. The subscript w typically has a value of 0 to 0.95, or 0.02 to 0.75, or 0.05 to 0.3, and the subscript x typically has a value of 0 to 0.95, or 0 to 0.7, or 0 to 0.25. The subscript y typically has a value of 0 to 1, 0.25 to 0.8, or 0.5 to 0.8, and the subscript z typically has a value of 0 to 0.95, or 0 to 0.7, Alternatively, it has a value of 0 to 0.15. The sum y + z is typically 0.05 to 1, 0.5 to 0.95, or 0.65 to 0.9. Further, the sum w + x is typically 0 to 0.95, or 0.05 to 0.5, or 0.1 to 0.35.

Typically, the group R in the silicone resin²At least 1 mol%, or at least 10 mol%, or at least 50 mol% of is a hydrogen, hydroxy, or hydrolyzable group.

Silicone resins typically have a number average molecular weight (M) of 500-50,000, or 500-10,000, or 1,000-3,000._n). Here, this molecular weight is measured by gel transmission chromatography using a small angle laser light scattering detector or a refractive index detector and a silicone resin (MQ) standard.

The viscosity of the silicone resin at 25 ° C is typically 0.01 to 100,000 Pa · s, 0.1 to 10,000 Pa · s, or 1 to 100 Pa · s.

Silicone resin is R¹R²₂SiO_1/2Units (ie M units) and / or R²₂SiO_2/2In combination with the unit (ie D unit), R²SiO_3/2Unit (ie T unit) R²SiO_3/2Units (ie T units) and SiO_4/2Unit (ie Q unit), or R²SiO_3/2Units (ie T units) and / or SiO_4/2Includes units (ie Q units) (in equation, R¹And R²Is as described and illustrated above). For example, the silicone resin can be a T resin, a TQ resin, a DT resin, an MT resin, an MDT resin, an MQ resin, a DQ resin, an MDQ resin, an MTQ resin, a DTQ resin or an MDTQ resin.

Examples of silicone resins include, but are not limited to, resins having the following formula: (MeSiO)_3/2)_n, (PhSiO_3/2)_n, (Me₃SiO_1/2)_0.8(SiO_4/2)_0.2, (MeSiO_3/2)_0.67(PhSiO_3/2)_0.33, (MeSiO_3/2)_0.45(PhSiO_3/2)_0.40(Ph₂SiO_2/2)_0.1(PhMeSiO_2/2)_0.05, (PhSiO_3/2)_0.4(MeSiO_3/2)_0.45(PhSiO_3/2)_0.1(PhMeSiO_2/2)_0.05, And (PhSiO_3/2)_0.4(MeSiO_3/2)_0.1(PhMeSiO_2/2)_0.5(In the formula, Me is methyl, Ph is phenyl, the subscript of the number outside the parentheses means mole fraction, and the subscript n is that this silicone resin has a number average molecular weight of 500 to 50,000. Has a value like). Further, in the above formula, the sequence of the above units is not specified.

A first embodiment of a condensation curable silicone composition can include a single silicone resin or a mixture containing two or more different silicone resins, each as described above.

Methods for preparing silicone resins containing hydrogen atoms, hydroxy groups or hydrolyzable groups bonded to silicon are well known in the art and many of these resins are commercially available. Silicone resins are typically prepared by co-hydrolyzing a suitable mixture of silane precursors in an organic solvent (eg, toluene). For example, silicone resin has the formula R¹R²₂Silane with SiX and formula R²SiX₃It can be prepared by co-hydrolyzing a silane having a silane in toluene (in the formula, R).¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarby, R²Is R¹, -H or a hydrolyzable group, and X is a hydrolyzable group, but R²If is a hydrolyzable group, then X is R in the hydrolyzing reaction.²More reactive). The hydrochloric acid and silicone hydrolyzate are separated, the hydrolyzate is washed with water to remove residual acid, heated in the presence of a mild condensation catalyst, and the resin is "thickened" to the required viscosity. (Body) "(ie, condensed). If desired, the resin can be further treated with a condensation catalyst in an organic solvent to reduce the content of hydroxy groups attached to silicon.

The first embodiment of the condensation curable silicone composition can contain additional components, but it has a low thermal expansion coefficient, high tensile strength and high modulus as the silicone resin cures, as described below. Only if the components do not prevent the formation of a cured silicone resin. Examples of additional components include adhesion promoters, dyes, dyes, antioxidants, heat stabilizers, UV stabilizers, flame retardants, fluidity adjusting additives, organic solvents, crosslinkers and condensation catalysts. Not limited to these.

For example, the silicone composition can further include a cross-linking agent and / or a condensation catalyst. The cross-linking agent is formula R³_qSiX_4-qCan have (in the formula, R³Is C₁~ C₈Hydrocarbyl or C₁~ C₈Halogen-substituted hydrocarbyls, where X is a hydrolyzable group and q is 0 or 1). R³The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by, and the hydrolyzable groups represented by X are as described and exemplified above.

An example of a cross-linking agent is an alkoxysilane (eg MeSi (OCH)₃)₃, CH₃Si (OCH₂CH₃)₃, CH₃Si (OCH₂CH₂CH₃)₃, CH₃Si [O (CH)₂)₃CH₃]₃, CH₃CH₂Si (OCH₂CH₃)₃, C₆H₅Si (OCH₃)₃, C₆H₅CH₂Si (OCH₃)₃, C₆H₅Si (OCH₂CH₃)₃, CH₂= CHSi (OCH)₃)₃, CH₂= CHCH₂Si (OCH₃)₃, CF₃CH₂CH₂Si (OCH₃)₃, CH₃Si (OCH₂CH₂OCH₃)₃, CF₃CH₂CH₂Si (OCH₂CH₂OCH₃)₃, CH₂= CHSi (OCH)₂CH₂OCH₃)₃, CH₂= CHCH₂Si (OCH₂CH₂OCH₃)₃, C₆H₅Si (OCH₂CH₂OCH₃)₃, Si (OCH₃)_4、Si (OC₂H₅)₄And Si (OC₃H₇)₄), Organic acetoxysilane (eg CH₃Si (OCOCH₃)₃, CH₃CH₂Si (OCOCH₃)₃And CH₂= CHSi (OCOCH)₃)₃), Organic iminooxysilane (eg CH₃Si [ON = C (CH)₃) CH₂CH₃]₃, Si [ON = C (CH)₃) CH₂CH₃]₄And CH₂= CHSi [ON = C (CH)₃) CH₂CH₃]₃), Organic acetamide silane (eg CH₃Si [NHC (= O) CH₃]₃And C₆H₅Si [NHC (= O) CH₃]₃), Aminosilane (eg CH₃Si [NH (sC)₄H₉)]₃And CH₃Si (NHC₆H₁₁)₃), As well as organic aminooxysilanes, but not limited to these.

The cross-linking agent may be a single silane or a mixture of two or more different silanes (each as described above). Further, methods for preparing trifunctional and tetrafunctional silanes are well known in the art, and many of these silanes are commercially available.

If present, the concentration of the cross-linking agent in the silicone composition is sufficient to cure (cross-link) the silicone resin. The exact amount of the cross-linking agent depends on the desired degree of curing, but the amount depends on the silicon in the cross-linking agent with respect to the number of moles of hydrogen atoms, hydroxy or hydrolyzable groups attached to the silicon in the silicone resin. It generally increases as the proportion of moles of attached hydrolyzable groups increases. Typically, the concentration of the cross-linking agent is sufficient to provide 0.2-4 mol of silicon-bonded hydrolyzable groups per mole of silicon-bonded hydrogen atoms, hydroxy groups or hydrolyzable groups in the silicone resin. Amount. The optimum amount of cross-linking agent can be easily determined by routine testing.

As mentioned above, the first embodiment of the condensation curable silicone composition can further comprise at least one condensation catalyst. The condensation catalyst may be any condensation catalyst typically used to facilitate the condensation of silicon-bonded hydroxy (silanol) groups to form Si-O-Si bonds. Examples of condensation catalysts include, but are not limited to, complexes of amines, carboxylic acids with lead, tin, zinc and iron. In particular, the condensation catalyst can be selected from tin (II) and tin (IV) compounds (eg tin dilaurate, tin dioctylate and tetrabutyltin), and titanium compounds (eg titanium tetrabutoxide).

If present, the concentration of the condensation catalyst is typically 0.1-10% (weight / weight), or 0.5-5% (weight / weight), or 1-3% (weight / weight), based on the total weight of the silicone resin. Weight / weight).

According to the second embodiment, the condensation-curable silicone composition has the formulas (A) (i) (R).¹R⁴₂SiO_1/2)_w(R⁴₂SiO_2/2)_x(R⁴SiO_3/2)_y(SiO_4/2)_zAn organosilicon compound selected from a silicone resin having (II) and a hydrolyzable precursor of (ii) (i), and formula R.⁵₃SiO (R¹R⁵SiO)_mSiR⁵₃A silicone-modified silicone resin prepared by reacting a silicone rubber having (III) in the presence of water, a condensation catalyst and an organic solvent to form a soluble reaction product (in the formula, R).¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyl and R⁴Is R¹, -OH or hydrolyzable group, R⁵Is R¹Or a hydrolyzable group, m is 2 to 1,000, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, z is 0 to 0.95, w + x + y + z = 1, y + z is 0.05 to 1, and w + x is 0 to 0.95, however, the silicone resin (II) is bonded to at least two silicons on average per molecule. Silicone rubber (III) has an average of at least two silicon-bonded hydrolyzable groups per molecule, and the silicone rubber (III) has a hydroxy or hydrolyzable group bonded to silicon in the silicone resin (II). The molar ratio of the hydrolyzable group bonded to silicon in the silicone rubber (III) to the hydrolyzable group is 0.01 to 1.5), and (B) a condensation catalyst are included.

The component (A) is the equation (i) (R).¹R⁴₂SiO_1/2)_w(R⁴₂SiO_2/2)_x(R⁴SiO_3/2)_y(SiO_4/2)_zAn organosilicon compound selected from at least one silicone resin having (II) and a hydrolyzable precursor of (ii) (i), and formula R⁵₃SiO (R¹R⁵SiO)_mSiR⁵₃A rubber-modified silicone resin prepared by reacting at least one silicone rubber having (III) with water, a condensation catalyst and an organic solvent to form a soluble reaction product. (In the formula, R¹, W, x, y, z, y + z and w + x are as described and exemplified above for silicone resins having formula (I), R.⁴And R⁵The hydrolyzable group represented by is R²As described and exemplified above, and m has a value of 2 to 1,000, except that silicone resin (II) has an average of at least two silicon-bonded hydroxy or hydrolyzable groups per molecule. However, silicone rubber (III) has an average of at least two silicon-bonded hydrolyzable groups per molecule, and silicone rubber (III) has a hydroxy or hydrolyzable group bonded to silicon in the silicone resin (II). The molar ratio of hydrolyzable groups bonded to silicon in) is 0.01 to 1.5). As used herein, the term "soluble reaction product" means that the product of the reaction for preparing component (A) is miscible with its organic solvent and does not form a precipitate or suspension. Means.

Typically, the group R in the silicone resin (i)⁴At least 10 mol%, or at least 50 mol%, or at least 80 mol% of is a hydroxy or hydrolyzable group.

Silicone resin (i) typically has a number average molecular weight (M) of 500-50,000, 500-10,000, or 1,000-3,000._n), Where this molecular weight is measured by gel permeation chromatography using a small angle laser light scattering detector, or a refraction index detector and a silicone resin (MQ) standard.

The viscosity of the silicone resin (i) at 25 ° C is typically 0.01 to 100,000 Pa · s, 0.1 to 10,000 Pa · s, or 1 to 100 Pa · s.

Silicone resin (i) is R¹R⁴₂SiO_1/2Units (ie M units) and / or R⁴₂SiO_2/2In combination with the unit (ie D unit), R⁴SiO_3/2Unit (ie T unit), R⁴SiO_3/2Units (ie T units) and SiO_4/2Unit (ie Q unit), or R⁴SiO_3/2Units (ie T units) and / or SiO_4/2Includes units (ie Q units) (in equation, R¹And R⁴Is as described and illustrated above). For example, this silicone resin can be T resin, TQ resin, DT resin, MT resin, MDT resin, MQ resin, DQ resin, MDQ resin, MTQ resin, DTQ resin or MDTQ resin.

Examples of silicone resins suitable for use as silicone resins (i) include, but are not limited to, resins having the following formulas: (MeSiO)_3/2)_n, (PhSiO_3/2)_n, (PhSiO_3/2)_0.4(MeSiO_3/2)_0.45(PhSiO_3/2)_0.1(PhMeSiO_2/2)_0.05, And (PhSiO_3/2)_0.3(SiO_4/2)_0.1(Me₂SiO_2/2)_0.2(Ph₂SiO_2/2)_0.4(In the formula, Me is methyl, Ph is phenyl, the subscript of the number outside the parentheses means mole fraction, and the subscript n is that this silicone resin has a number average molecular weight of 500 to 50,000. Has a value like). Moreover, in the above-mentioned formula, the array of units is not specified.

The silicone resin (i) may be a single silicone resin or a mixture containing two or more different silicone resins, each of which has the formula (II).

Methods for preparing silicone resins suitable for use as silicone resins (i) are well known in the art and many of these resins are commercially available. For example, silicone resins are typically prepared by co-hydrolyzing a suitable mixture of silane precursors in an organic solvent (eg, toluene), as described above for silicone resins of formula (I). Toluene.

The organosilicon compound may be a (ii) hydrolyzable precursor of a silicone resin having the formula (II). As used herein, the term "hydrolyzable precursor" refers to a hydrolyzable group suitable for use as a starting material (precursor) for the preparation of silicone resins having formula (II). Refers to the silane that has. This hydrolyzable precursor is of formula R¹R⁴₂SiX, R⁴₂SiX₂, R⁴SiX₃And SiX₄Can be expressed by (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyl and R⁴Is R¹Or it is a hydrolyzable group, and X is a hydrolyzable group). Examples of hydrolyzable precursors include, but are not limited to, silanes having the following formulas: Me₂ViSiCl, Me₃SiCl, MeSi (OEt)₃, PhSiCl₃, MeSiCl₃, Me₂SiCl₂, PhMeSiCl₂, SiCl₄, Ph₂SiCl₂, PhSi (OMe)₃, MeSi (OMe)₃, PhMeSi (OMe)₂, And Si (OEt)₄(In the formula, Me is methyl, Et is ethyl, and Ph is phenyl).

Methods for preparing silanes with hydrolyzable groups are well known in the art and many of these compounds are commercially available.

In the silicone rubber formula (III), R¹And R⁵Is described and illustrated above, and the subscript m typically has a value of 2 to 1,000, or 4 to 500, or 8 to 400.

Examples of silicone rubbers having formula (III) include, but are not limited to, silicone rubbers having the following formulas: (EtO).₃SiO (Me₂SiO)₅₅Si (OEt)₃, (EtO)₃SiO (Me₂SiO)₁₆Si (OEt)₃, (EtO)₃SiO (Me₂SiO)₃₈₆Si (OEt)₃And (EtO)₂MeSiO (PhMeSiO)₁₀SiMe (OEt)₂(In the formula, Me is methyl and Et is ethyl).

The silicone rubber having the formula (III) may be a single silicone rubber or a mixture containing two or more different silicone rubbers each having the formula (III). For example, this silicone rubber comprises a first silicone rubber having a dp (degree of polymerization) of about 15 (represented by the value of m in Formula III) and a second silicone rubber having a dp of about 350. be able to.

Methods for preparing silicone rubbers containing hydrolyzable groups bound to silicon are well known in the art and many of these compounds are commercially available.

The condensation catalyst used in the preparation of the rubber-modified silicone resin of the component (A) is as described and exemplified above for the first embodiment of the condensation curable silicone composition. In particular, the titanium compound is a suitable condensation catalyst used in the preparation of component (A).

The organic solvent is at least one organic solvent. The organic solvent does not react with the organosilicon compound, silicone rubber or silicone resin modified with rubber under the conditions for preparing the component (A) (described later), and is compatible with the above-mentioned components. It can be any aprotic or bipolar aprotic organic solvent.

Examples of organic solvents include saturated aliphatic hydrocarbons (eg n-pentane, hexane, n-heptane, isooctane and dodecane), alicyclic hydrocarbons (eg cyclopentane and cyclohexane), aromatic hydrocarbons (eg benzene, etc.). Toluene, xylene and mesitylene), cyclic ethers (eg tetrahydrofuran (THF) and dioxane), ketones (eg methylisobutylketone (MIBK)), alkane halides (eg trichloroethane), and halogenated aromatic hydrocarbons (eg bromobenzene and bromobenzene). Chlorobenzene), but is not limited to these. The organic solvent may be a single organic solvent or a mixture containing two or more different organic solvents, each as described above.

The organosilicon compound, silicone rubber, condensation catalyst and organic solvent can be mixed in any order. Typically, the organosilicon compound, silicone rubber and organic solvent are mixed prior to the introduction of the condensation catalyst.

The molar ratio of the hydrolyzable group bonded to silicon in the silicone rubber to the hydroxy or hydrolyzable group bonded to silicon in the silicone resin having the formula (II) is typically 0.01 to 1.5 or 0.05 to 0.8. , Or 0.2 to 0.5.

The concentration of water in the reaction mixture is the group R in the organosilicon compound.⁴Depends on the properties of the hydrolyzable group bonded to silicon in the silicone rubber. When the organosilicon compound contains hydrolyzable groups, the concentration of water is sufficient to cause hydrolysis of the hydrolyzable groups in the organosilicon compound and the silicone rubber. For example, the concentration of water is typically 0.01-3 mol, or 0.05-1 mol, per mol of hydrolyzable groups in the combined organosilicon compound and silicone rubber. If the organosilicon compound does not contain hydrolyzable groups, only trace amounts (eg 100 ppm) of water are required in the reaction mixture. Trace amounts of water are usually present in reactants and / or solvents.

The concentration of the condensation catalyst is a concentration sufficient to catalyze the condensation reaction between the organosilicon compound and the silicone rubber. Typically, the concentration of the condensation catalyst is 0.01-2% (weight / weight), 0.01-1% (weight / weight), or 0.05-0.2% (weight / weight), based on the weight of the organosilicon compound. ).

The concentration of the organic solvent is typically 10-95% (weight / weight), or 20-85% (weight / weight), or 50-80% (weight / weight), based on the total weight of the reaction mixture. ).

The reaction is typically carried out at room temperature (about 23 ± 2 ° C) to 180 ° C, or room temperature to 100 ° C.

The reaction time depends on several factors, including the structure and temperature of the organosilicon compounds and silicone rubber. The components can typically react for a period of time sufficient to complete the condensation reaction. is this,²⁹Constituting at least 95 mol%, or at least 98 mol%, or at least 99 mol% of the silicon-bonded hydrolyzable groups originally present in the silicone rubber when measured by Si NMR spectroscopy until consumed in the condensation reaction. Ingredients mean that they can react. The reaction time is typically 1-30 hours at room temperature (about 23 ± 2 ° C) to 100 ° C. Optimal reaction times can be determined in routine tests using the methods described in the Examples section below.

The rubber-modified silicone resin can be used in the second embodiment of the condensation curable silicone composition without isolation or purification, or the resin can be used in most solvents by conventional methods of vaporization. It can also be separated from. For example, the reaction mixture may be heated under reduced pressure.

The component (B) of the second embodiment of the condensation curable silicone composition is at least one condensation catalyst, which catalyst is as described and exemplified above for the first embodiment of the silicone composition. Is. In particular, zinc compounds and amines are suitable for use as constituents (B) of the silicone compositions of the present invention.

The concentration of component (B) is typically 0.1-10% (weight / weight), 0.5-5% (weight / weight), or 1-3, based on the weight of component (A). % (Weight / Weight).

A second embodiment of the condensation curable silicone composition can contain additional components, which are that the silicone resin is cured and has a low thermal expansion coefficient, high tensile strength and high modulus as described below. Only if the components do not prevent the formation of a cured silicone resin. Examples of additional ingredients include, but are limited to, adhesion promoters, dyes, dyes, antioxidants, heat stabilizers, UV stabilizers, flame retardants, fluidity adjusting additives, crosslinkers and organic solvents. Not done.

For example, a second embodiment of a condensation curable silicone composition is of formula R.³_qSiX_4-qCan further include cross-linking agents having (in the formula, R).³, X, and q are as described and exemplified above for the cross-linking agent of the first embodiment). The cross-linking agent can be a single silane or a mixture of two or more different silanes (each as described above).

If present, the concentration of the cross-linking agent in the second embodiment of the condensation-curable silicone composition is sufficient to cure (cross-link) the rubber-modified silicone resin of component (A). is there. The exact amount of the cross-linking agent depends on the desired degree of curing, but the amount depends on the number of moles of silicon-bonded hydroxy or hydrolyzable groups in the silicon-modified silicone resin in the cross-linking agent. It generally increases as the proportion of moles of hydrolyzable groups attached to silicon increases. Typically, the concentration of the cross-linking agent provides 0.2-4 mol of silicon-bonded hydrolyzable groups per mole of silicon-bonded hydroxy or hydrolyzable groups in the rubber-modified silicone resin. Enough amount for. The optimum amount of cross-linking agent can be easily determined by routine testing.

Curable compositions comprising thermosetting polymers can further comprise carbon nanomaterials, which are described and exemplified above. If present, the carbon nanomaterial is typically 0.0001 to 99% (weight / weight), or 0.001 to 50% (weight / weight), or 0.01 to 0.01, based on the total weight of the thermosetting polymer. It has a concentration of 25% (weight / weight), or 0.1-10% (weight / weight), or 1-5% (weight / weight).

The release liner may be coated with a curable composition comprising a thermosetting polymer using conventional coating techniques such as spin coating, dipping, spraying, brushing, extrusion or screen printing. The amount of the composition is sufficient to form a first polymer layer having a thickness of 0.01-1000 μm after the polymer has been cured in step (ii) of the method described below.

In step (ii) of the method immediately prior to forming the first polymer layer, the thermosetting polymer of the coated release liner is cured. Thermosetting polymers can be cured using a variety of methods, such as room temperature, high temperature, moisture or radiation, depending on the type of curable composition used to coat the release liner. Is to be exposed to.

If the curable composition used to coat the release liner is a condensation-curable silicone composition containing at least one silicone resin having an average of at least two silicone-bonded hydroxy groups per molecule, it was coated. The silicone resin of the release liner can be cured by heating the coating at a temperature sufficient to cure the silicone resin. For example, silicone resins can be cured by heating the coating, typically at a temperature of 50 to 250 ° C. for 1 to 50 hours. When the condensation curable silicone composition comprises a condensation catalyst, the silicone resin can typically be cured at a lower temperature, for example room temperature (about 23 ± 2 ° C) to 200 ° C.

The curable composition used to coat the release liner is at least one silicone resin having hydrogen atoms bonded to at least two silicons on average per molecule (eg, of the first embodiment of the condensation curable silicone composition). In the case of a silicone resin) containing a condensation curable silicone composition, the silicone resin can be cured by exposing the coating to moisture or oxygen for 0.1 to 20 hours at a temperature of 100 to 450 ° C. When the condensation-curable silicone composition comprises a condensation catalyst, the silicone resin can typically be cured at a lower temperature, for example room temperature (about 23 ± 2 ° C) to 400 ° C.

Further, when the curable composition used for coating the release liner is a condensation curable silicone composition containing at least one silicone resin having a hydrolyzable group bonded to at least two silicons on average per molecule. The silicone resin can be cured by exposing the coating to moisture for 1 to 100 hours at room temperature (about 23 ± 2 ° C) to 250 ° C, or 100 to 200 ° C. For example, silicone resins can typically be cured by exposing the coating to a temperature of approximately room temperature (about 23 ± 2 ° C) to 150 ° C for 0.5 to 72 hours at 30% relative humidity. Curing can be accelerated by heating, exposure to high humidity and / or addition of a condensation catalyst to the composition.

Silicone resins can be cured at atmospheric pressure or pressures below atmospheric pressure. For example, if the coating is not surrounded between two release liners, the silicone resin is typically cured at atmospheric pressure in the air. Alternatively, if the coating is enclosed between a first and second release liner (discussed below), the silicone resin is typically cured under reduced pressure. For example, the silicone resin can be heated under a pressure of 1,000 to 20,000 Pa, or 1,000 to 5,000 Pa. Silicone resin is a traditional vacuum bagging process Can be cured under reduced pressure using process). In a typical process, a bleeder (eg polyester) is applied over a coated release liner and a breather (eg nylon, polyester) is applied over this bleeder for a vacuum bag with a vacuum nozzle. A film (eg nylon) is applied over this breather, this assembly is tape sealed, a vacuum (eg 1,000 Pa) is applied to the sealed assembly, and if necessary, the vacuumed assembly is as described above. Is heated to.

The method of forming the first polymer layer containing the thermosetting polymer is to apply a second release liner to the coated release liner of the first step after step (i) and before step (ii). The steps of forming the assembly and compressing the assembly can be further included. This assembly can be compressed to remove excess composition and / or invading air and reduce the thickness of the coating. The assembly can be compressed using conventional equipment (eg stainless steel rollers, hydraulic presses, rubber rollers or laminated roll sets). The assembly is compressed at a temperature of room temperature (about 23 ± 2 ° C) to 50 ° C, typically at a pressure of 1,000 Pa to 10 MPa.

If the same curable composition is used in each coating step, the method of forming a first polymer layer containing a thermosetting polymer repeats steps (i) and (ii) to increase the thickness of the polymer layer. Further steps can be included.

If the first polymer layer contains a thermoplastic polymer and a fiber reinforced material, the polymer layer is (a) impregnated with the fiber reinforced material in a composition containing the thermoplastic polymer in a fluid state, and (b) impregnated. It can be formed by the step of converting the thermoplastic polymer of the fiber reinforced material into a solid state.

In step (a) of the method immediately prior to forming the first polymer layer, the fiber reinforced material is impregnated in a composition comprising a fluidized thermoplastic polymer.

The fiber reinforced material can be impregnated in a composition comprising a fluidized thermoplastic polymer using various methods. For example, according to the first method, the fiber reinforced plastic is formed by (i) applying a composition containing a thermoplastic polymer in a fluid state to a release liner to form a film, and (ii) applying the fiber reinforced plastic to the film. It can be impregnated by embedding and (iii) applying the above composition to the embedded fiber reinforcing material to form an impregnated fiber reinforcing material.

In step (i) of the method immediately prior to impregnating the fiber reinforced material, the composition containing the thermoplastic polymer in the fluid state is applied to a release liner to form a film. The release liner and composition are as described and exemplified above. The composition can be applied to the release liner using conventional coating techniques such as spin coating, dipping, spraying, brushing, extrusion or screen printing. The composition is applied in an amount sufficient to embed the fiber reinforced plastic in the following step (ii).

In step (ii), the fiber reinforced material is embedded in the film. The fiber reinforcing material is as described and illustrated above. The fiber reinforcing material can be embedded in the film by simply placing the reinforcing material on the film and allowing the composition of the film to saturate the reinforcing material.

In step (iii), the composition comprising the fluidized thermoplastic polymer is applied to the embedded fiber reinforced material to form an impregnated fiber reinforced plastic. The composition can be applied to the embedded fiber reinforced plastic using conventional methods, as described above for step (i).

The first method of impregnating the fiber reinforcing material further includes (iv) applying a second release liner to the impregnated fiber reinforcing material to form an assembly, and (v) compressing the assembly. be able to. The first method is to remove gas from the embedded fiber reinforced plastic after step (ii) and before step (iii), and / or after step (iii) and step (iii). Before iv), a step of removing gas from the impregnated fiber reinforced plastic can be further included.

The assembly can be compressed to remove excess composition and / or air that has entered and reduce the thickness of the impregnated fiber reinforced plastic. The assembly can be compressed using conventional equipment (eg stainless steel rollers, hydraulic presses, rubber rollers or laminated roll sets). The assembly is compressed at a temperature of room temperature to 200 ° C, typically at a pressure of 1,000 Pa to 10 MPa.

The embedded or impregnated fiber reinforced material can be degassed by exposing it to vacuum at a temperature sufficient to maintain the fluid state of the thermoplastic polymer.

Alternatively, according to the second method, the fiber reinforcing material is obtained by (i) placing the fiber reinforcing material on a release liner, (ii) embedding the fiber reinforcing material in a composition containing a thermoplastic polymer in a fluid state, and then. (iii) By applying the above composition to the embedded fiber reinforcing material to form an impregnated fiber reinforcing material, it can be impregnated in a composition containing a thermoplastic polymer in a fluid state. The second method can further include (iv) applying a second release liner to the impregnated fiber reinforced material to form an assembly, and (v) compressing the assembly. In the second method, steps (iii)-(v) are as described above for the first method of impregnating the composition containing the fluidized thermoplastic polymer with the fiber reinforcement. The second method is to remove the gas from the embedded fiber reinforced plastic after the step (ii) and before the step (iii), and / or after the step (iii) and the step. Prior to (iv), a step of removing gas from the impregnated fiber reinforced plastic can be further included.

In step (ii) of the method immediately prior to impregnating the fiber reinforced material, the fiber reinforced material is embedded in a composition containing a fluidized thermoplastic polymer. The fiber reinforcing material can be embedded in the composition by simply covering the reinforcing material with the composition and saturating the reinforcing material in the composition.

Further, if the fiber reinforcement is a woven or non-woven fabric, the reinforcement can be impregnated in the composition by passing it through a composition containing a fluidized thermoplastic polymer. The cloth typically passes through the composition at a rate of 1-1,000 cm / min.

In step (b) of the method described above for forming the first polymer layer, the thermoplastic polymer of the impregnated fiber reinforced material is transformed into a solid state. If the composition used to coat the release liner contains a molten thermoplastic polymer, the thermoplastic polymer will have a liquid-solid transition temperature (T)._gOr T_m) It can be converted to a solid state by allowing the polymer to cool to a lower temperature, eg room temperature. If the composition used to coat the release liner comprises a thermoplastic polymer and an organic solvent, the thermoplastic polymer can be converted to a solid state by removing at least a portion of the solvent. The organic solvent can be removed by vaporizing the solvent at ambient temperature or by heating the coating to a moderate temperature, eg, below the solid-liquid transition temperature of the polymer.

The method of forming the first polymer layer containing the composition containing the thermoplastic resin in the fluid state and the fiber reinforcing material repeats steps (a) and (b) when the same composition is used for each impregnation. It can further include increasing the thickness of the polymer layer.

If the first polymer layer contains a thermosetting polymer and a fiber reinforced plastic, the polymer layer is (a') impregnated with the fiber reinforced plastic in a curable composition containing a thermosetting polymer and (b'). It can be formed by curing the thermosetting polymer of the impregnated fiber reinforced material.

In step (a') of the method immediately prior to forming the first polymer layer, the fiber reinforced material is impregnated in a curable composition comprising a thermosetting polymer. The fiber reinforced materials and compositions are as described and exemplified above. The fiber reinforced material can be impregnated in the curable composition using the above method for impregnating the fiber reinforced material in the composition containing the thermoplastic polymer.

In the step (b') of the method immediately before forming the first polymer layer, the thermosetting polymer of the impregnated fiber reinforced material is cured. Thermosetting polymers can be used in a variety of ways, including exposing the impregnated fiber reinforced plastic to room temperature or high temperature, moisture or radiation, depending on the type of curable composition used to impregnate the fiber reinforced plastic. Can be cured using.

If the curable composition used to impregnate the fiber reinforcement is a condensation-curable silicone composition containing at least one silicone resin having an average of at least two silicone-bonded hydroxy groups per molecule, the silicone. The resin can be cured by heating the impregnated fiber reinforcement at a temperature sufficient to cure the silicone resin. For example, silicone resins can typically be cured by heating the coating at a temperature of 50-250 ° C for 1-50 hours. When the condensation-curable silicone composition comprises a condensation catalyst, the silicone resin can typically be cured at a lower temperature, for example room temperature (about 23 ± 2 ° C) to 200 ° C.

The first embodiment of a first embodiment of a condensation-curable silicone composition (eg, a first embodiment of a condensation-curable silicone composition) in which the curable composition used to impregnate the fiber reinforcement has at least one silicone resin bonded to at least two silicons on average per molecule. In the case of a silicone composition containing (silicone resin), the silicone resin can be cured by exposing the impregnated fiber reinforcing material to water or oxygen for 0.1 to 20 hours at a temperature of 100 to 450 ° C. .. When the condensation curable silicone composition comprises a condensation catalyst, the silicone resin can typically be cured at a lower temperature, for example room temperature (about 23 ± 2 ° C) to 400 ° C.

Further, the curable composition used for impregnating the fiber reinforcing material is a condensation curable silicone composition containing at least one silicone resin having a hydrolyzable group bonded to at least two silicons on average per molecule. If the silicone resin is exposed to moisture for 1 to 100 hours at room temperature (about 23 ± 2 ° C) to 250 ° C, or 100 to 200 ° C. Can be cured. For example, silicone resins are typically obtained by exposing the impregnated fiber reinforced plastic to a relative humidity of 30% for 0.5 to 72 hours at a temperature of approximately room temperature (approximately 23 ± 2 ° C) to 150 ° C. Can be cured. Curing can be accelerated by heating, exposure to high humidity and / or addition of a condensation catalyst to the composition.

The impregnated silicone resin of the fiber reinforced material can be cured at atmospheric pressure or a pressure lower than atmospheric pressure, depending on the above method used for impregnating the fiber reinforced material in the condensation curable silicone composition. For example, if the coating is not surrounded between the first and second release liners, the silicone resin is typically cured in air at atmospheric pressure. Alternatively, if the coating is enclosed between the first and second release liners, the silicone resin is typically cured under reduced pressure. For example, the silicone resin can be heated under a pressure of 1,000 to 20,000 Pa, or 1,000 to 5,000 Pa. The silicone resin can be cured under reduced pressure using a conventional vacuum bag pressurization process. In a typical process, a bleeder (eg polyester) is applied over a coated release liner, a breather (eg nylon, polyester) is applied over this bleeder, and a vacuum bag film (eg nylon) with a vacuum nozzle is applied. The assembly is applied over the breather, the assembly is tape-sealed, a vacuum (eg 1,000 Pa) is applied to the sealed assembly, and if necessary, the evacuated assembly is heated as described above.

If the same curable composition is used for each impregnation, the method of preparing a first polymer layer containing a thermosetting polymer and a fiber reinforced material is to repeat steps (a') and (b') to make the polymer layer. A step of increasing the thickness of the material can be further included.

In the second step of the method of preparing the first reinforced silicone resin film, the second polymer layer described above is formed on the first polymer layer. The second polymer layer is formed as described above in the method of forming the first polymer layer, except that the second polymer layer is formed on the first polymer layer rather than the release liner. can do.

The method of preparing the first reinforced silicone resin film can further include the step of separating the first polymer layer from the release liner (single layer or multilayer). The first polymer layer can be separated from the release liner (one layer or multiple layers) either before or after the second polymer layer is formed. In addition, the first polymer layer can be separated from the release liner by mechanically stripping the layer from the release liner.

The second reinforced silicone resin film according to the present invention is With the first polymer layer, With the second polymer layer on the first polymer layer, With at least one additional polymer layer above at least one of the first and second polymer layers At least one of these polymer layers comprises a cured product of at least one silicone resin having a hydrogen atom, a hydroxy group or a hydrolyzable group bonded to at least two silicons on average per molecule. At least one of the polymer layers contains carbon nanomaterials.

The first polymer layer of the second reinforced silicone resin film typically has a thickness of 0.01 to 1000 μm, or 5 to 500 μm, or 10 to 100 μm.

The first polymer layer of the second reinforced silicone resin film can include a thermoplastic polymer or a thermosetting polymer. The thermoplastic polymer and the thermosetting polymer are as described and exemplified above for the first reinforced silicone resin film.

In addition to the thermoplastic or thermosetting polymer, the first polymer layer of the second reinforced silicone resin film is a carbon nanomaterial, a fiber reinforced material or a mixture thereof (as illustrated and exemplified above, respectively). Yes) can be included.

The second polymer layer and the additional polymer layer of the second reinforced silicone resin film are as described and exemplified above for the first polymer layer. Adjacent layers of the second reinforced silicone resin film differ in at least one of many physical and chemical properties, including thickness, polymer composition, crosslink density, concentration of carbon nanomaterials or concentration of additional components.

The second reinforced silicone resin film typically comprises 1-100 additional polymer layers, or 1-10 additional polymer layers, or 2-5 additional polymer layers.

At least one of the polymer layers of the second reinforced silicone resin film is a cured product of at least one silicone resin having an average of at least two silicon-bonded hydrogen atoms, hydroxy or hydrolyzable groups per molecule. including. The silicone resin, the method for preparing the resin, and the method for preparing the cured product of the silicone resin are as described above in the method for preparing the first reinforced silicone resin film of the present invention.

At least one of the polymer layers of the second reinforced silicone resin film contains carbon nanomaterials. The carbon nanomaterial, the concentration of the carbon nanomaterial and the method for preparing the carbon nanomaterial are as described and exemplified above for the first reinforced silicone resin film.

The first polymer layer, the second polymer layer and the additional polymer layer can be prepared as described later in the method for preparing the second reinforced silicone resin film of the present invention.

The second reinforced silicone resin film is The process of forming the first polymer layer on the release liner, The process of forming the second polymer layer on top of the first polymer layer, With the step of forming at least one additional polymer layer on at least one of the first and second polymer layers At least one of these polymer layers is a cured product of at least one silicone resin having a hydrogen atom, a hydroxy group or a hydrolyzable group bonded to at least two silicons on average per molecule. And at least one of the polymer layers can be prepared by a method comprising carbon nanomaterials.

The first polymer layer, the second polymer layer and the additional polymer layer can be formed as described above in the method of preparing the first reinforced silicone resin film.

The reinforced silicone resin films of the present invention typically have 1-99% (weight / weight), or 10-95% (weight / weight), or 30-95% (weight / weight), or 50-95%. Contains (weight / weight) cured silicone resin. The reinforced silicone resin film typically has a thickness of 1 to 3000 μm, or 15 to 500 μm, or 15 to 300 μm, or 20 to 150 μm, or 30 to 125 μm.

Reinforced silicone resin films are typically made of cylindrical steel mandrel whose flexibility is measured as described in ASTM Standard D522-93a, Method B, where the film has a diameter of 3.2 mm or less. It has the flexibility to be able to bend on it without cracking.

Reinforced silicone resin films have a low coefficient of linear thermal expansion (CTE), high tensile strength, high modulus of elasticity and high resistance to thermally induced cracks. For example, this film is typically 0-80 μm / m ° C, or 0-20 μm / m ° C, or 2-10 μm / m at room temperature (approximately 23 ± 2 ° C) to 200 ° C. It has a CTE of ° C. The film also typically has a tensile strength of 5 to 200 MPa, or 20 to 200 MPa, or 50 to 200 MPa at 25 ° C. In addition, this reinforced silicone resin film typically has a Young's modulus of 0.5-10 GPa, or 1-6 GPa, or 3-5 GPa at 25 ° C.

The transparency of a reinforced silicone resin film depends on many factors such as the composition of the cured silicone resin, the thickness of the film, and the type and concentration of the reinforced material. The reinforced silicone resin film typically has at least 5%, or at least 10%, or at least 15%, or at least 20% transparency (% transmittance) in the visible region of the electromagnetic spectrum.

The reinforced silicone resin film of the present invention is useful for applications that require a film with high thermal stability, flexibility, mechanical strength and transparency. For example, this silicone resin film can be used as an integral part of flexible displays, solar cells, flexible electronic circuit boards, touch screens, fire resistant wallpaper and impact resistant windows. This film is also a suitable substrate for transparent or opaque electrodes.

<p> The following examples are shown to better illustrate the reinforced silicone resin films and methods of the invention, but these should be considered limiting the invention as described in detail in the appended claims. is not it. Unless otherwise stated, in the examples, the number of copies and percentages reported are by weight. The following materials were used in the examples.</p><p> Pyrograf®-III Grade HHT-19 Carbon Nanofibers, commercially available from Pyrograf Products, Inc. (Cedarville, Ohio), are 100-200 nm in diameter and long. Heat-treated (up to 3000 ° C) carbon nanofibers with a dimension of 30,000 to 100,000 nm.</p><p> Commercially available from SDC Technologies, Inc. (Anaheim, CA), SDC MP101 Crystal Coat Resin contains methanol, 2-propanol, water and acetic acid (approximately 1-2%). ) In essentially MeSiO_3/2Unit and SiO_4/2A solution containing 31% (weight / weight) of a silicone resin consisting of units.</p><p> Glass Fabric is a heat-treated glass fabric prepared by heating a style 106 electric glass fabric with a plain weave and a thickness of 37.5 μm at 575 ° C for 6 hours. The untreated glass cloth was obtained from JPS Glass (Slater, South Carolina).</p><p> (Example) This example shows the preparation of chemically oxidized carbon nanofibers. Pyrograph®-III carbon nanofibers (2.0 g), 12.5 mL concentrated nitric acid and 37.5 mL concentrated sulfuric acid, cooler, thermometer, Teflon® coated magnetic stir bar and temperature controller Sequentially mixed in a 500 mL three-necked flask provided. The mixture was heated to 80 ° C and kept at this temperature for 3 hours. The mixture was then cooled by placing the flask on a layer of dry ice in a 1 gallon bucket. The mixture was poured into a Büchner funnel containing a nylon membrane (0.8 μm) and carbon nanofibers were collected by vacuum filtration. The nanofibers remaining on the membrane were washed several times with deionized water until the pH of the filtrate was equal to the pH of the wash water. After the final wash, the carbon nanofibers were kept in the funnel for an additional 15 minutes with subsequent application of vacuum. The nanofibers supported on the filter membrane were then placed in the oven at 100 ° C. for 1 hour. The carbon nanofibers were removed from the filter membrane and stored in a dry, sealed glass jar.</p><p> (Example 2) Oxidized carbon nanofibers (0.031 g) of Example 1 and 50.0 g of SDC MP101 crystal coated resin were mixed in a glass vial. The vial was placed in an ultrasonic bath for 30 minutes. The mixture was then centrifuged at 2000 rpm for 30 minutes. The supernatant composition was used to prepare a reinforced silicone resin film, as described below.</p><p> (Example 3) A glass cloth (38.1 cm x 8.9 cm) was impregnated with MP101 crystal coated resin by passing the cloth through the composition at a rate of about 5 cm / sec. The impregnated cloth was then hung vertically in a ventilation hood at room temperature to dry and then cured in an air circulation oven according to the following cycle: 75 ° from room temperature to 75 ° C at 1 ° C / min. 1 hour at C, 75 ° C to 100 ° C at 1 ° C / min, 1 hour at 100 ° C, and 100 ° C to 125 ° C at 1 ° C / min, 1 hour at 125 ° C .. The oven was switched off and the silicone resin film was allowed to cool to room temperature.</p><p> This film was impregnated with a silicone composition prepared by diluting the carbon nanofiber-filled silicone composition of Example 2 with 2-propanol to a resin of 20.75% (weight / weight). The impregnated cloth was then dried and cured as described above after the first impregnation.</p><p> This three-layer reinforced silicone resin film was then heat treated in a nitrogen atmosphere oven under the following conditions: room temperature to 575 ° C at 5 ° C / min, 1 hour at 575 ° C. The oven was switched off and the reinforced silicone resin film was allowed to cool to room temperature. Fi before heat treatment a microscopic photograph of Lum, shown in FIG. 1A (top view) and FIG. 1B (sectional view). A photomicrograph of the reinforced silicone resin film after heat treatment is shown in FIG. 1C. This heat-treated film has no cracks.</p><p> (Comparative example 1) The method of Example 3 except that the second impregnation was performed using a silicone composition prepared by diluting MP101 crystal coated resin with 2-propanol to a resin of 20.75% (weight / weight). A non-reinforced silicone resin film was prepared according to the above.</p><p> After curing, this 3-layer silicone resin film was heat treated in an air circulation oven under the following conditions: room temperature to 400 ° C at 5 ° C / min, 1 hour at 400 ° C. The oven was switched off and the film was allowed to cool to room temperature. Micrographs of the silicone resin film before and after the heat treatment are shown in FIGS. 2A and 2B, respectively. This heat treated film contains many cracks.</p><p> (Example 4) The second impregnation was performed using a silicone composition prepared by diluting the carbon nanofiber-filled silicone composition of Example 2 with 2-propanol to a resin of 10.35% (weight / weight). Except for the above, a reinforced silicone resin film was prepared according to the method of Example 3.</p><p> After curing, this 3-layer reinforced silicone resin film was heat treated in a nitrogen atmosphere oven under the following conditions: room temperature to 575 ° C at 5 ° C / min, 575 ° C for 1 hour at 575 ° C. The oven was switched off and the film was allowed to cool to room temperature. A photomicrograph of the reinforced silicone resin film after the heat treatment is shown in FIG. This heat-treated film is crack-free.</p><p> (Example 5) The reinforced silicone resin film prepared according to the method of Example 3 was impregnated with the silicone composition prepared by diluting MP101 crystal coat resin with 2-propanol to 10.35% (weight / weight) of the resin. The film was dried and cured as described in Example 3.</p><p> This 5-layer reinforced silicone resin film was heat treated in a nitrogen atmosphere oven under the following conditions: 5 ° C / min from room temperature to 575 ° C, 575 ° C for 1 hour. The oven was switched off and the film was allowed to cool to room temperature. A photomicrograph of the reinforced silicone resin film after the heat treatment is shown in FIG. This film is crack-free.</p><p> (Comparative example 2) The method of Example 3 except that the second impregnation was performed using a silicone composition prepared by diluting MP101 Crustal Coat Resin with 2-propanol to a resin of 10.35% (weight / weight). A non-reinforced silicone resin film was prepared according to the above. The cured three-layer silicone resin film was then impregnated with the rediluted MP101 Crustal Coat Resin. The film was dried and cured as described in Example 3.</p><p> This 5-layer silicone resin film was heat treated in a nitrogen atmosphere oven under the following conditions: room temperature to 575 ° C at 5 ° C / min, 1 hour at 575 ° C. The oven was switched off and the film was allowed to cool to room temperature. Observed using a light microscope and a magnification of 100x, approximately 14% of the surface area of this film contained microcracks prior to heat treatment. After heat treatment, almost 55% of the surface area of the film contained microcracks.</p>