Fabric sheet, release material for heat sealing machine, and release agent composition

Abstract

To provide a fabric sheet not containing a fluororesin, preventing the seizure of the heater of a heat sealing machine and a plastic film, excellent in releasability, slip properties and flexibility and suitable as a release material for the heat sealing machine.SOLUTION: The fabric sheet has a cured product of a composition containing (B) an organopolysiloxane having a structure represented by the following average composition formula (I) on the surface and / or inside of (A) a woven fabric or a nonwoven fabric composed of a heat-resistant fiber. (In the formula, R1 and R2 each independently represent a C1-12 alkyl group or the like, k represents an integer of 1 to 3, m represents a number of 5 to 100, n represents 1 to 3, R3, R4, and R5 each independently represent a C1-12 alkyl group or the like, and a, b, c, d, e, and f represent numbers satisfying 0 ≤ a <1, 0 <b ≤ 1, 0 ≤ c <1, 0 <d ≤ 1, 0 <e ≤ 1, 0 ≤ f <1, and a + b + c + d + e + f = 1.). ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fabric sheet or the like that is effectively used as a release material for a heat-sealing machine, prevents sticking between a heater (heat source) and a plastic film, and has excellent release properties (non-stickiness), slip properties (friction properties), and flexibility (softness). [Background technology]

[0002] Conventionally, the lamination of plastic films, such as polyethylene films and polypropylene films, has been commonly performed by a so-called heat sealing method, in which a heater such as a metal heater maintained at a temperature higher than the welding temperature of the film is pressed against the film to weld it. In this case, it is known that the heater is surface-treated to have releasability to prevent adhesion between the heater and the film. For example, Patent Documents 1 and 2 propose attaching a fluororesin tape, which is made by applying a fluororesin dispersion to a woven fabric (such as glass cloth) made of heat-resistant fibers and baking it onto the surface of a heat dissipation bar, to prevent the plastic film from baking onto the surface of the heat dissipation bar.

[0003] Patent Document 3 proposes a release sheet that is resistant to microcracks and has excellent durability, which is made by sequentially providing a glass fiber cloth, a silicone resin layer, and a polytetrafluoroethylene (hereinafter abbreviated as PTFE) layer.

[0004] The fluororesins, typified by PTFE, used in these fluororesin tapes and release sheets are known to have excellent heat and cold resistance, electrical insulation, chemical resistance, non-stickiness (release properties), weather resistance, and friction properties, and are used in the above-mentioned applications by taking advantage of these properties. On the other hand, fluororesins, commonly known as PFAS (perfluoroalkyl and polyfluoroalkyl compounds), are being considered for regulation, primarily in the EU, due to concerns about their environmental persistence and bioaccumulation, and in recent years there has been a growing desire to replace them. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-203529 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-231110 [Patent Document 3] Japanese Patent Application Publication No. 1-314165 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to provide a fabric sheet that does not contain a fluororesin, prevents seizure between the heater of a heat sealing machine and a plastic film, and has excellent releasability (non-stickiness), slipperiness (friction properties), and flexibility (softness), and a release material for a heat sealing machine that uses the same. [Means for solving the problem]

[0007] In order to achieve the above object, the present inventors have conducted extensive research and have found that the following fabric sheet can solve the above problems, thereby completing the present invention. That is, the present invention provides the following fabric seat etc. [1] (A) On the surface and / or inside of a woven or nonwoven fabric made of heat-resistant fibers, (B) A cured product of a composition containing an organopolysiloxane having a structure represented by the following average composition formula (I): A fabric seat having [ka] (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms, k represents an integer of 1 to 3, m represents a number of 5 to 100, and n represents a number of 1 to 3; R 3 、R 4 and R 5 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxy group, and a, b, c, d, e and f represent numbers satisfying 0 ≦ a < 1, 0 < b ≦ 1, 0 ≦ c < 1, 0 < d ≦ 1, 0 < e ≦ 1, 0 ≦ f < 1, and a + b + c + d + e + f = 1.) [2] The fabric sheet according to [1], wherein (B) further contains (C) silicone powder. [3] The fabric sheet according to [2], wherein the silicone powder of (C) is resin powder. [4] In the above formula (I), a = 0, R 2 is a methyl group, and n = 2. The fabric sheet according to any one of [1] to [3]. [5] (A) The amount of (B) per 1 m 2 is 10 to 300 g / m 2 The fabric sheet according to any one of [1] to [4]. [6] The fabric sheet according to any one of [1] to [5], wherein the heat-resistant fiber of (A) is glass fiber. [7] A release material for a heater of a heat-sealing machine using the fabric sheet according to any one of [1] to [6]. [8] (B') An organopolysiloxane having a structure represented by the following average composition formula (I) [Chemical formula] (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms, k represents an integer of from 1 to 3, m represents a number of from 5 to 100, and n represents from 1 to 3, R 3 、R 4 and R 5 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxy group, and a, b, c, d, e and f represent numbers satisfying 0 ≦ a < 1, 0 < b ≦ 1, 0 ≦ c < 1, 0 < d ≦ 1, 0 < e ≦ 1, 0 ≦ f < 1, and a + b + c + d + e + f = 1.) and (C) silicone powder A release agent composition containing

Advantages of the Invention

[0008] The fabric sheet of the present invention has no concerns about environmental persistence and bioaccumulation, which were problems of conventional fluororesin tapes and fluororesin fabric sheets, prevents sticking of the heater and the plastic film in the heat-sealing machine, and has excellent releasability (non-stickiness), slipperiness (friction characteristics), and flexibility (softness), and thus is suitably used as a release material for heat-sealing machines. Further, the release agent composition of the present invention has no concerns about environmental persistence and bioaccumulation, does not contain a fluororesin, and is suitably used as a material excellent in releasability and the like for release materials for heat-sealing machines and the like.

Modes for Carrying Out the Invention

[0009] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. [Fabric Sheet] The fabric sheet of the present invention has a cured product of a composition containing (B) an organopolysiloxane having a structure represented by the average composition formula (I) on the surface and / or inside of a woven fabric or non-woven fabric made of (A) heat-resistant fibers. The cured product of the composition containing (B) an organopolysiloxane having a structure represented by the average composition formula (I) may further contain (C) silicone powder. First, the components (A) to (C) constituting the fabric sheet of the present invention will be described. For ease of explanation, the "organopolysiloxane having a structure represented by average composition formula (I)" may be referred to as (B') to distinguish it from the "cured product of a composition containing (B) an organopolysiloxane having a structure represented by average composition formula (I)."

[0010] (A) Woven or nonwoven fabric made of heat-resistant fibers The woven or nonwoven fabric made of heat-resistant fibers (A) used in the present invention is used as the core material of the fabric sheet of the present invention. Examples of the woven fabric made of heat-resistant fibers include plain, satin, or twill woven fabrics made of at least one type of fiber selected from glass fibers, carbon fibers, aramid resin fibers, polyimide resin fibers, phenolic resin fibers, silicon carbide fibers, silicon nitride fibers, and stainless steel fibers. The thickness of the heat-resistant fibers used in the woven fabric is preferably 5 to 200 tex, and the weave density of the woven fabric is preferably 5 to 200 threads / 25 mm vertically and 5 to 200 threads / 25 mm horizontally, with a mass of 10 to 300 g / m 2 The thickness is preferably 0.01 to 0.5 mm.

[0011] Examples of nonwoven fabrics made of heat-resistant fibers include nonwoven fabrics made of at least one type of fiber selected from glass fiber, carbon fiber, aramid resin fiber, polyimide resin fiber, phenolic resin fiber, and polyparaphenylenebenzobisoxazole fiber. As the woven or nonwoven fabric made of these heat-resistant fibers, commercially available products can be used.

[0012] (B) Cured product The components that can be contained in the composition containing the organopolysiloxane (B') having a structure represented by average composition formula (I), which becomes the cured product (B) of the fabric sheet of the present invention, will be described below.

[0013] (B') Organopolysiloxane having a structure represented by average composition formula (I): The organopolysiloxane (B') has a structure represented by the following average composition formula (I). [ka]

[0014] Above, R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms. Specific examples of alkyl groups having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-decyl group, and an n-dodecyl group. Specific examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Among these, R 1 and R 2 As the alkyl group, a methyl group, an ethyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, or a phenyl group is preferable, a methyl group, an ethyl group, or a phenyl group is more preferable, and a methyl group is even more preferable.

[0015] Above, R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group. Specific examples of alkyl groups having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-decyl group, and an n-dodecyl group. Specific examples of the alkenyl group having 2 to 8 carbon atoms include a vinyl group, an allyl group, a 3-butenyl group, a 5-hexenyl group, and a 7-octenyl group. Specific examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a naphthyl group, etc. Specific examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group, a phenylethyl group, etc. Specific examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an i-butoxy group, etc. Among these, R 3 、R 4 and R 5 are preferably a methyl group, an ethyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a phenyl group, more preferably a methyl group, an ethyl group, a phenyl group, and still more preferably a methyl group.

[0016] k is an integer of 1 to 3, preferably 3. m is a number of 5 to 100, preferably 5 to 50, more preferably 5 to 30. n is an integer of 1 to 3, preferably 2.

[0017] a, b, c, d, e and f are numbers satisfying 0 ≦ a < 1, 0 < b ≦ 1, 0 ≦ c < 1, 0 < d ≦ 1, 0 < e ≦ 1, 0 ≦ f < 1, and a + b + c + d + e + f = 1. a is a number satisfying 0 ≦ a < 1, but from the viewpoints of the non-sticking property (release property), friction property, and flexibility (softness) of the obtained sheet, 0 ≦ a ≦ 0.5 is preferable, and 0 ≦ a ≦ 0.2 is more preferable. b is a number satisfying 0 < b ≦ 1, but from the viewpoints of the non-sticking property (release property), friction property, and flexibility (softness) of the obtained sheet, 0.01 ≦ b ≦ 0.5 is preferable, and 0.01 ≦ b ≦ 0.3 is more preferable. c is a number satisfying 0 ≦ c < 1, but from the viewpoints of the non-sticking property (release property), friction property, and flexibility (softness) of the obtained sheet, 0 ≦ c ≦ 0.4 is preferable, and 0 ≦ c ≦ 0.3 is more preferable. d is a number satisfying 0 < d ≦ 1, but from the viewpoints of the non-sticking property (release property), friction property, and flexibility (softness) of the obtained sheet, 0 < d ≦ 0.8 is preferable, and 0.1 ≦ d ≦ 0.6 is more preferable. e is a number satisfying 0 < e ≤ 1. From the viewpoints of the non-stickiness (release property), frictional properties, and flexibility (softness) of the resulting sheet, 0.1 ≤ e ≤ 0.8 is preferable, and 0.1 ≤ e ≤ 0.6 is more preferable. f is a number satisfying 0 ≤ f < 1. From the viewpoints of the non-stickiness (release property), frictional properties, and flexibility (softness) of the resulting sheet, 0 ≤ f ≤ 0.5 is preferable, and 0 ≤ f ≤ 0.2 is more preferable.

[0018] (B’) The organopolysiloxane can be synthesized by a general hydrolysis-condensation reaction and hydrosilylation reaction. For example, an oligomer (c1) obtained by hydrolytically condensing a monomer containing a silane compound having a hydrolyzable group such as an alkenyl group and an alkoxysilyl group, a linear organohydrogenpolysiloxane (a1) having a SiH group at one end and an alkoxysilyl group at the other end, and a linear organohydrogenpolysiloxane (b1) having SiH groups at both ends can be obtained by a hydrosilylation reaction. By reacting (c1) with (b1), the film-forming property and flexibility (softness) of the resulting organopolysiloxane are improved. Further, by reacting (a1) in addition to (b1), the reactivity (curing property) of the resulting organopolysiloxane can be improved. In addition, an organic solvent may be used during the hydrolysis-condensation. Specific examples of the organic solvent that can be used include methanol, ethanol, propanol, acetone, methyl ethyl ketone, tetrahydrofuran, toluene, xylene, and the like.

[0019] Also, if a large amount of unreacted (a1) and (b1) remains in the reaction product, the SiH group may decompose over time to generate flammable hydrogen gas, or the physical properties and performance of (B’) may change over time. Therefore, it is preferable to completely react (a1) and (b1). For this reason, the ratio of the total number of SiH groups contained in (a1) and (b1) to the number of alkenyl groups contained in the above oligomer (c1) is preferably in the range of [number of alkenyl groups] / [number of SiH groups] = 1.1 to 10, and more preferably in the range of 1.2 to 5. A specific example of a method for producing the organopolysiloxane (B') is the method described in International Publication No. 2023-157603.

[0020] (B') may be either a solid or a liquid, but is preferably a liquid from the viewpoint of ease of handling, etc. When (B') is a liquid, the kinematic viscosity at 25°C is 100 to 10,000 mm 2 / s is preferable, and 100 to 2,000 mm 2 / s is more preferable, 200 to 1,000 mm 2 / s is more preferable, and 300 to 800 mm 2 / s is most preferred. When (B') is a solid, it can be diluted with an organic solvent in which (B') dissolves, such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, butyl cellosolve, methyl cellosolve, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, etc. It can also be used by dispersing (B') in water using a surfactant or the like to form an emulsion. The kinematic viscosity mentioned above is a value measured at 25°C using a Cannon-Fenske viscometer according to the method described in JIS Z 8803:2011 (the same applies hereinafter). The weight average molecular weight (Mw) of (B') in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably from 1,000 to 50,000, more preferably from 5,000 to 20,000.

[0021] Other ingredients in (B) (C) Silicone powder The (B) cured product may further contain (C) a silicone powder in addition to the (B') organopolysiloxane having a structure represented by average composition formula (I). That is, the (B') cured product, which is a composition containing an (B') organopolysiloxane having a structure represented by average composition formula (I), may contain (C) a silicone powder. Conventional silicone powders can be used, including resin powders made from polymethylsilsesquioxane, polymethylphenylsilsesquioxane (copolymer), polyphenylsilsesquioxane, etc.; rubber powders made from crosslinked dimethylpolysiloxane; and composite powders in which rubber powder surfaces are coated with silicone resin. Examples of resin powders include KMP-590, X-52-854, X-52-1621, and KMP-592 (manufactured by Shin-Etsu Chemical Co., Ltd.), and Tospearl 120, Tospearl 130, Tospearl 145, and Tospearl 1110 (manufactured by Momentive Performance Materials Japan, LLC). Examples of rubber powders include KMP-402, KMP-597, and KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), DOWSIL TREFIL E-506S Silicone Powder, and DOWSIL EP-9215 Cosmetic Powder (manufactured by Dow Chemical Japan). Examples of composite powders include KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, and KSP-105 (manufactured by Shin-Etsu Chemical Co., Ltd.). From the viewpoint of dispersibility in (B), resin powders and composite powders are preferred, and from the viewpoint of ease of availability, resin powders are more preferred. The amount of silicone powder blended is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, and even more preferably 3 to 40 parts by mass, per 100 parts by mass of component (B'). If the amount of silicone powder is less than 1 part by mass, sufficient effects in terms of releasability (non-stickiness) and slipperiness (friction characteristics) cannot be obtained. If the amount is more than 100 parts by mass, the viscosity of the mixture becomes too high, reducing coatability, making the fabric sheet more susceptible to defects such as voids (air gaps), and reducing the flexibility (pliability) of the cured product, making the fabric sheet more susceptible to breakage or cracks. The silicone powder may be used alone or in combination of two or more types.

[0022] ·catalyst A catalyst can be used to accelerate the curing of (B'). This catalyst is not particularly limited as long as it is one that is commonly used in the condensation curing reaction of organosiloxanes, but organometallic compounds are preferred, such as metal alkoxide compounds of Ti, Al, Zr, Zn, Sn, etc., metal chelate compounds, and metal ester compounds.

[0023] Specific examples of the metal alkoxide compound include aluminum alkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, and aluminum tri-t-butoxide; titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-t-butyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, and tetra-n-lauryl titanate; tetraethyl zirconate, tetra-n-propyl zirconate, and tetraisopropyl zirconate; Examples of the alkoxides include zirconium alkoxides such as tetra-n-butyl zirconate, tetraisobutyl zirconate, tetra-t-butyl zirconate, tetra-n-pentyl zirconate, tetra-t-pentyl zirconate, tetra-n-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, and tetra-n-stearyl zirconate; zinc alkoxides such as zinc dimethoxide, zinc diethoxide, zinc dipropoxide, zinc dibutoxide, zinc dihexylate, zinc dioctylate, zinc didesylate, zinc didodecylate, zinc ditetradecylate, zinc dihexadecylate, zinc dioctadecylate, zinc diphenolate, zinc ditolylate, and zinc dixylate; and tin alkoxides such as dibutyltin dibutoxide.

[0024] Specific examples of metal chelate compounds include aluminum tris(ethylacetoacetate), aluminum tris(n-propylacetoacetate), aluminum tris(isopropylacetoacetate), aluminum tris(n-butylacetoacetate), aluminum tris(acetylacetonato), aluminum tris(propionylacetonato), aluminum dipropoxypropionylacetonato, aluminum acetylacetonato bis(propionylacetonato), aluminum monoethylacetoacetate bis(acetylacetonato), aluminum acetylacetonato di-s-butylate, aluminum methylacetoacetate di-s-butylate, aluminum di(methylacetoacetate) mono-t-butylate, and aluminum di-s-butylate. Examples of suitable chelate compounds include aluminum chelate compounds such as diisopropoxyethyl acetoacetate aluminum and monoacetylacetonato bis(ethylacetoacetate)aluminum; titanium chelate compounds such as diisopropoxy bis(ethylacetoacetate)titanate, diisopropoxy bis(acetylacetonato)titanate, di-n-butoxy bis(acetylacetonato)titanate, lactate titanate, ammonium lactate titanate, and triethanolamine titanate; zirconium chelate compounds such as tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)zirconium, and tetrakis(ethylacetoacetate)zirconium; and tin chelate compounds such as dibutyltin bis(acetylacetonate).

[0025] Specific examples of metal ester compounds include aluminum ester compounds such as aluminum 2-ethylhexanoate; zirconium ester compounds such as zirconium 2-ethylhexanoate; zinc ester compounds such as zinc 2-ethylhexanoate; and tin ester compounds such as dibutyltin diacetate, dibutyltin di(2-ethylhexyl)ate, dibenzyltin di(2-ethylhexyl)ate, dibutyltin dilaurate, and dibutyltin diisooctylmaleate.

[0026] Among these, the catalyst is preferably one containing an organic titanium compound such as a titanium alkoxide compound or a titanium chelate compound, more preferably one containing a titanium chelate compound from the viewpoint of curing reactivity, and even more preferably one containing only a titanium chelate compound. Commercially available titanium chelate compounds can also be used, such as D-20, D-25, and D-26 (manufactured by Shin-Etsu Chemical Co., Ltd.), Orgatix TC-750, and Orgatix TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.).

[0027] The amount of catalyst added is preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (B'). If the amount of catalyst is less than 0.1 part by mass, curability will be insufficient, and if it is more than 15 parts by mass, the pot life after adding the catalyst will be too short. The catalyst may be used alone or in combination of two or more.

[0028] Other additives Specific examples of additives include adhesion promoters such as non-reactive silicone oils, reactive silicone oils, and silane coupling agents, non-reactive polymer resins, fillers, leveling agents, rheology modifiers, reactive diluents, non-reactive diluents, surfactants, dispersants, antifoaming agents, dehydrating agents, antioxidants, antioxidants, heat resistance improvers, antistatic agents, infrared absorbers, ultraviolet absorbers, light stabilizers, fluorescent agents, dyes, pigments, fragrances, abrasives, rust inhibitors, and thixotropy-imparting agents. These may be used alone or in combination of two or more, and the blending amounts thereof are selected from the appropriate amounts for each. The proportion of (B') in the total of all components in the composition containing (B') is preferably 50 to 100 mass %, more preferably 60 to 98 mass %, and even more preferably 70 to 97 mass %.

[0029] (B') an organopolysiloxane having a structure represented by average composition formula (I) and any other optional ingredients are mixed in the above amounts by a known method and cured to obtain (B) as a cured composition containing (B') an organopolysiloxane having a structure represented by average composition formula (I). An example of a specific curing method will be described later in the fabric sheet manufacturing method.

[0030] [Fabric seat manufacturing method] The fabric sheet of the present invention can be produced by applying or impregnating a woven fabric or nonwoven fabric made of heat-resistant fibers (A) with a composition containing (B'), and then curing the composition under specified conditions, thereby producing a fabric sheet having a cured product of the composition containing (B') on the surface and / or inside of the woven fabric or nonwoven fabric made of heat-resistant fibers (A).

[0031] The method for applying or impregnating the composition containing (B') into (A) is not particularly limited, and various known methods can be appropriately used, for example, various printing methods such as gravure printing, offset printing, gravure offset printing, flexographic printing, and screen printing, and various known methods such as gravure coating, microgravure coating, roll coating, rod coating, kiss coating, knife coating, air knife coating, comma coating, die coating, lip coating, flow coating, dip coating, and spray coating.

[0032] In the fabric sheet of the present invention, (A) 1 m of woven or nonwoven fabric made of heat-resistant fibers 2 The amount of the cured product (B) per unit area is preferably 10 to 300 g / m 2 , more preferably 20 to 200 g / m 2 , and more preferably 30 to 100 g / m 2 is. That is, the amount of the composition containing (B') is, for example, preferably 10 to 300 g / m 2 in terms of the solid content after drying. 2 , more preferably 20 to 200 g / m 2 , and more preferably 30 to 100 g / m 2It is preferable to coat or impregnate the surface and / or interior of (A) with an amount that satisfies the above range. If the amount is within this range, the resulting fabric sheet has appropriate flexibility and is less likely to break or crack, which is preferable.

[0033] The curing conditions for the composition containing (B') may include leaving it at room temperature for a long period of time to cure, but it is generally cured by drying and / or reacting it through heat treatment. Examples of heat sources for the heat treatment include hot air dryers, infrared heaters, and rotary dryers. Heating conditions include a temperature of 80 to 180°C, preferably 100 to 150°C, and a time of 0.1 to 180 minutes, more preferably 1 to 30 minutes.

[0034] [Release material for heaters in heat sealing machines] After curing, a sheet-like molded product is obtained as a fabric sheet having the cured product (B) on the surface and / or inside of (A), and this may be used as a release material for the heater of a heat-sealing machine as is, or may be processed into a tape by coating one side with an adhesive.

[0035] [Release agent composition] Next, a release agent composition containing (B') an organopolysiloxane having a structure represented by the average composition formula (I) above and (C) a silicone powder will be described. Specific examples of (B') and (C) contained in the release agent composition of the present invention are the same as those described above for the fabric sheet. In addition to (B') and (C), the release agent composition of the present invention may contain the above-mentioned catalyst and other additives. The blending amount of the silicone powder (C) in the release agent composition is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, and even more preferably 3 to 40 parts by mass, per 100 parts by mass of the component (B'). The amount of the catalyst in the release agent composition is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of (B'). The amount of the other additives to be added to the release agent composition is selected from the appropriate amounts depending on the type of the additives. The proportion of (B') in the entire release agent composition is preferably from 50 to 99 mass %, more preferably from 60 to 98 mass %, and even more preferably from 70 to 97 mass %. The release agent composition of the present invention, when applied to a mold in a resin molding process and cured, turns into a cured film with mold-releasability, making it a durable release agent for repeated use. Furthermore, because the cured film has flexibility, it can adapt to thermal expansion and contraction, making it a crack-resistant release agent. [Example]

[0036] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0037] In the examples, the kinematic viscosity was measured at 25°C using a Cannon-Fenske viscometer according to the method described in JIS Z 8803:2011. The molecular weight was determined as a weight average molecular weight (Mw) converted into polystyrene by measurement using a GPC (gel permeation chromatography) device manufactured by Tosoh Corporation, using toluene as a solvent and RI as a detector. The ratio of the constituent units of (B) organopolysiloxane was measured using a 300 MHz-NMR measurement device manufactured by JEOL Ltd. 1 H-NMR and 29 It was calculated from the integral value of the detected spectrum in Si-NMR. The vinyl group content (mol / 100 g, hereinafter referred to as vinyl value) was quantified by treating each product with Hanus's solution, then reacting it with an aqueous potassium iodide solution, and titrating the resulting iodine with sodium thiosulfate.

[0038] [Explanation of each ingredient] (A) Woven or nonwoven fabric made of heat-resistant fibers Commercially available glass cloth (plain weave, 50 g / m 2An ultra-thin, dense plain woven micro glass cloth (#50) with a thickness of 0.045 mm, purchased from Featherfield Co., Ltd., was purchased and used for the evaluation.

[0039] (B') Organopolysiloxane R2: Synthesized by the method described in Synthesis Example 2 below. R3: Synthesized by the method described in Synthesis Example 3 below. R4: Synthesized by the method described in Synthesis Example 4 below (for comparative example). R5: Synthesized by the method described in Synthesis Example 5 below (for comparative example).

[0040] (C) Silicone powder KMP-590: Resin powder, average particle size 2 μm, manufactured by Shin-Etsu Chemical Co., Ltd. X-52-854: Resin powder, average particle size 0.7 μm, manufactured by Shin-Etsu Chemical Co., Ltd. X-52-1621: Resin powder, average particle size 5 μm, manufactured by Shin-Etsu Chemical Co., Ltd. KMP-592: Phenyl resin powder, average particle size 2 μm, manufactured by Shin-Etsu Chemical Co., Ltd. KSP-105: Composite powder, average particle size 2 μm, manufactured by Shin-Etsu Chemical Co., Ltd. KMP-600: Composite powder, average particle size 5 μm, manufactured by Shin-Etsu Chemical Co., Ltd.

[0041] (catalyst) D-20: Titanium chelate compound, manufactured by Shin-Etsu Chemical Co., Ltd.

[0042] [Synthesis Example 1] A 2-L three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 740 g (1.54 mol) of methyltrimethoxysilane, 160 g (0.27 mol) of vinylmethyldimethoxysilane, and 0.28 g of maleic anhydride. 34.7 g of ion-exchanged water was added dropwise with stirring at 15°C, and the reaction was carried out at 70°C for 3 hours. Subsequently, 6 g of cation exchange resin (Lewatit K2629, manufactured by LANXESS) was added, and the reaction was carried out for an additional 3 hours at 70°C. The resulting reaction solution was distilled under atmospheric pressure, and once no more distillate was produced, it was heated at 105°C for 3 hours. Finally, the distillate was removed under reduced pressure (90°C, 1.3 kPa), yielding organopolysiloxane compound (R1: yield 580 g). The resulting organopolysiloxane compound (R1) was a colorless, transparent liquid with a kinematic viscosity of 66 mmHg. 2 / s, vinyl number 0.15 mol / 100 g, Mw=3,100. The organopolysiloxane compound (R1) was represented by the following average composition formula: [(Me)SiO 3 / 2 ] 0.85 [(Me)(Vi)SiO 2 / 2 ] 0.15 Me represents a methyl group, and Vi represents a vinyl group.

[0043] [Synthesis Example 2] 265 g of organopolysiloxane compound (R1) and 160 g of organohydrogenpolysiloxane represented by the following formula (II) were mixed in a 500 mL three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer. The reaction molar ratio of vinyl groups to Si-H groups was 4:1. While stirring the mixture in the flask at 80°C, 0.0004 moles of Pt(0) 1,3-divinyltetramethyldisiloxane complex relative to the Si-H groups was added, and the reaction was carried out at 80°C for 3 hours. The fraction was then removed by vacuum distillation (90°C, 1.3 kPa), yielding 420 g of a colorless, transparent liquid, organopolysiloxane compound (R2). The resulting organopolysiloxane compound (R2) had a kinematic viscosity of 200 mm 2 / s, Mw=12,000. The ratio of the structural units in the formula (I) of the organopolysiloxane compound (R2) is a=0, b=0.01, c=0, d=0.85, e=0.14, f=0, m=39, n=2, R 2 = methyl group, R 3 = methyl group, R 4 = methyl and vinyl groups. [ka]

[0044] [Synthesis Example 3] A 500 mL three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 230 g of organopolysiloxane compound (R1), 100 g of an organohydrogenpolysiloxane represented by the following formula (III), and 95 g of an organohydrogenpolysiloxane represented by the following formula (IV). The reaction molar ratio of vinyl groups to Si-H groups was 4:1. While stirring the mixture in the flask at 80°C, a 1,3-divinyltetramethyldisiloxane complex of Pt(0) was added in an amount equivalent to 0.0004 moles relative to the Si-H groups, and the reaction was carried out at 80°C for 3 hours. The fraction was then removed by vacuum distillation (90°C, 1.3 kPa), yielding 418 g of a colorless, transparent liquid, organopolysiloxane compound (R3). The resulting organopolysiloxane compound (R3) had a kinematic viscosity of 300 mm 2 / s, Mw=12,000. The ratio of the structural units in the formula (I) of the organopolysiloxane compound (R3) is a=0.01, b=0.01, c=0, d=0.85, e=0.13, f=0, k=3, m=18, n=2, R 1 = methyl group, R 2 = methyl group, R 3 = methyl group, R 4 = methyl and vinyl groups. [ka]

[0045] [Synthesis Example 4] A 2L three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 221g (1.63 mol) of methyltrimethoxysilane, 156g (0.79 mol) of phenyltrimethoxysilane, 40g of isopropyl alcohol, and 182g of xylene. While stirring at 15°C, 12g of methanesulfonic acid and 121g of water were added, and the reaction was carried out at 70°C for 3 hours. The mixture in the flask was cooled to below 50°C, neutralized with 12g of sodium bicarbonate, and 280g of xylene was added. The by-product methanol and other fractions were removed by atmospheric distillation (80°C). The resulting solution was washed with water to remove the neutralization salt, and then distilled at atmospheric pressure (120°C) and reduced pressure (70°C, 1.3 kPa) to remove the fractions. Xylene was added to adjust the nonvolatile content (150°C, 30 minutes) to 50%, and then the mixture was filtered to obtain a 50% xylene solution of organopolysiloxane compound (R4). The resulting organopolysiloxane compound (R4) had Mw=8,000. The organopolysiloxane compound (R4) was represented by the following average composition formula: [(Me)SiO 3 / 2 ] d1 [(Ph)SiO 3 / 2 ] d2 d1+d2=1.00, d1:d2=67:33

[0046] [Synthesis Example 5] A 2 L three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 1155 g of warm water at 70 °C. A mixture of 247 g of toluene, 106 g of hexane, 77 g (0.60 mol) of dimethyldichlorosilane, 63 g (0.42 mol) of methyltrichlorosilane, 4 g (0.02 mol) of diphenyldichlorosilane, and 156 g (0.74 mol) of phenyltrichlorosilane was added over 90 minutes, followed by polymerization at 70 °C for 30 minutes. After cooling the mixture to below 50 °C, the lower layer of water was removed, and the remaining upper layer was washed by repeatedly adding and removing water until the pH was neutral. The resulting solution was subjected to azeotropic dehydration (120 °C, atmospheric pressure) and vacuum distillation (70 °C, 1.3 kPa) to remove the remaining water. Xylene was added to adjust the nonvolatile content (150°C, 30 minutes) to 60%, and then the mixture was filtered to obtain a 60% xylene solution of organopolysiloxane compound (R5). The resulting organopolysiloxane compound (R5) had Mw=6,500. The organopolysiloxane compound (R5) was represented by the following average composition formula: [(Me)SiO 3 / 2 ] d1 [(Ph)SiO 3 / 2 ] d2 [(Me)SiO 2 / 2 ] e1 [(Ph)2SiO 2 / 2 ] e2 d1+d2=0.65, d1:d2=35:65, e1+e2=0.35, e1:e2=96:4

[0047] [Example 1] A coating liquid was prepared by adding 2 g of the curing catalyst D-20 to 20 g of the organopolysiloxane compound (R2) and further mixing. The coating liquid obtained had a deposition amount of approximately 40 g / m after heat curing. 2 The mixture was applied to a glass cloth by knife coating so as to have the following composition, and then cured by heating at 150°C for 60 minutes to prepare a fabric sheet (F1).

[0048] [Example 2] A coating solution was prepared by mixing 19 g of organopolysiloxane compound (R2) and 1 g of KMP-590, adding 2 g of curing catalyst D-20, and further mixing. The coating solution obtained had a deposition weight of approximately 40 g / m after heat curing. 2 The mixture was applied to a glass cloth by knife coating so as to have the following composition, and then cured by heating at 150°C for 60 minutes to prepare a fabric sheet (F2).

[0049] [Examples 3 to 11] In each example, fabric sheets (F3 to F11) were produced in the same manner as in Example 1 using the formulations shown in Table 1 or Table 2.

[0050] [Comparative Example 1] A coating solution was prepared by mixing 32 g of a 50% xylene solution of organopolysiloxane compound (R4) (16 g of R4) and 4 g of KMP-590, and adding 2 g of curing catalyst D-20. The coating solution obtained had a deposition weight of approximately 40 g / m after heat curing. 2 The mixture was applied to a glass cloth by knife coating so as to have the following composition, and then cured by heating at 150°C for 60 minutes to prepare a fabric sheet (F12).

[0051] Comparative Example 2 A coating solution was prepared by mixing 26.7 g (16 g of R5) of a 60% xylene solution of organopolysiloxane compound (R5) with 4 g of KMP-590, and adding 2 g of curing catalyst D-20. The coating solution obtained had a deposition weight of approximately 40 g / m after heat curing. 2 The mixture was applied to a glass cloth by knife coating so as to have the following composition, and then cured by heating at 150°C for 60 minutes to prepare a fabric sheet (F13).

[0052] Comparative Example 3 A commercially available fluororesin fabric sheet (As One, FGF400-3) was purchased and used for the evaluation.

[0053] [Evaluation items and methods] Polyethylene (PE) mold release A test piece was prepared by sandwiching a piece of polyethylene sheet (1 cm wide strip) between two fabric sheets (2 cm wide strips) and pressing them with an iron at 200°C for 3 minutes. The fabric sheet on one side was then peeled off in a 180° direction, and the peel force was measured, and the PE releasability was evaluated according to the following criteria. ◎: Less than 0.1N ○: 0.1~0.2N △: 0.2~0.3N ×:0.3~0.4N ××: Over 0.4N

[0054] Slipperiness The dynamic friction force between the fabric sheets was measured at 25°C according to the method described in JIS K 7125:1999, and the slipperiness was evaluated according to the following criteria. ◎: Less than 0.4N ○: 0.4~0.6N △: 0.6~0.8N ×:0.8~1.0N ××: More than 1.0N

[0055] flexibility The fabric sheet was visually inspected for creases and cracks when bent. ○: No breaks or cracks △: A few breaks and cracks ×: Many breaks and cracks occur

[0056] [Table 1]

[0057] [Table 2]

[0058] [Table 3]

[0059] As shown in Tables 1 and 2, it was found that the fabric sheets F1 to F11 of Examples 1 to 11 had good PE releasability and slipperiness, and were free from cracks and creases when bent, showing excellent flexibility. On the other hand, as shown in Table 3, it was found that the fabric sheets F12 and F13 of Comparative Examples 1 and 2 were poor in PE releasability, slipperiness, and flexibility. The commercially available fluororesin fabric sheet of Comparative Example 3 had good PE releasability, slipperiness, and flexibility, but had problems due to the inclusion of fluororesin.

Claims

1. (A) on the surface and / or inside of a woven or nonwoven fabric made of heat-resistant fibers, (B) A cured product of a composition containing an organopolysiloxane having a structure represented by the following average composition formula (I): A fabric seat having 【Chemistry 1】 (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms, k represents an integer of 1 to 3, m represents a number of 5 to 100, and n represents a number of 1 to 3; R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group, and a, b, c, d, e, and f represent numbers that satisfy 0≦a<1, 0<b≦1, 0≦c<1, 0<d≦1, 0<e≦1, 0≦f<1, and a+b+c+d+e+f=1.

2. The fabric sheet according to claim 1, wherein (B) further contains (C) a silicone powder.

3. 3. The fabric sheet according to claim 2, wherein the silicone powder (C) is a resin powder.

4. In the formula (I), a=0, R 2 The fabric sheet according to claim 1, wherein n is a methyl group and n=2.

5. (A) 1 m 2 The amount of (B) per 2 The fabric sheet according to claim 1,

6. 2. The fabric sheet according to claim 1, wherein the heat-resistant fiber (A) is glass fiber.

7. A release material for a heater in a heat sealing machine, which uses the fabric sheet according to any one of claims 1 to 6.

8. (B') an organopolysiloxane having a structure represented by the following average composition formula (I): 【Chemistry 2】 (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms, k represents an integer of 1 to 3, m represents a number of 5 to 100, and n represents a number of 1 to 3; R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group, and a, b, c, d, e, and f represent numbers that satisfy 0≦a<1, 0<b≦1, 0≦c<1, 0<d≦1, 0<e≦1, 0≦f<1, and a+b+c+d+e+f=1. and (C) Silicone powder A mold release agent composition comprising:

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