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

Abstract

Provided is a fabric sheet which is suitable as a mold release material for a heat sealing meachine, said fabric sheet not including a fluororesin, preventing searing of a plastic film and a heater of the heat sealing machine, and excelling in a mold release property, a sliding property, and flexibility. The fabric sheet comprises, on the surface and / or the inside of (A) a woven or nonwoven fabric composed of heat-resistant fibers, (B) a cured product of a composition including an organopolysiloxane having a structure represented by average compositional formula (I). (In the formula, R1 and R2 each independently represent a 1-12C alkyl group or the like; k represents an integer 1-3; m represents a number 5-100; n represents 1-3; R3, R4, and R5 each independently represent a 1-12C 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.)

Description

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

[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 seizure between a heater (heat source) and a plastic film, and has excellent release properties (non-stickiness), slip properties (friction properties), and flexibility (softness).

[0002] Conventionally, the lamination of plastic films, such as polyethylene films and polypropylene films, has been generally 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 in order 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] Furthermore, Patent Document 3 proposes a release sheet that is resistant to microcracks and has excellent durability, which is formed by sequentially providing a glass fiber cloth, a silicone resin layer, and a polytetrafluoroethylene (hereinafter abbreviated as PTFE) layer.

[0004] Fluororesins, such as 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, so-called PFAS (perfluoroalkyl compounds and polyfluoroalkyl compounds), are being considered for regulation mainly in the EU due to concerns about their environmental persistence and bioaccumulation, and replacement has been desired in recent years.

[0005] JP 2000-203529 A JP 2013-231110 A JP 1-314165 A

[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.

[0007] In order to achieve the above object, the present inventors conducted extensive research and found that the following fabric sheet can solve the above problems, leading to the completion of the present invention. That is, the present invention provides the following fabric sheet, etc.: [1] A fabric sheet having, on the surface and / or inside of (A) 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): (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 an integer of 1 to 3; R ３ , R ４ and R ５ each independently represent 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 [1], wherein (B) further contains (C) a silicone powder. [3] The fabric sheet according to [2], wherein the silicone powder (C) is a resin powder. [4] In the formula (I), a=0, R ２ [5] (A) 1m ２ The amount of (B) per ２[6] The fabric sheet according to any one of [1] to [5], wherein the heat-resistant fiber (A) is a glass fiber. [7] A release material for a heater in 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): (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 an integer of 1 to 3; R ３ , R ４ and R ５ each independently represent 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.

[0008] The fabric sheet of the present invention is free from the concerns of environmental persistence and bioaccumulation that have been problems with conventional fluororesin tapes and fluororesin fabric sheets, prevents seizure between the heater and the plastic film in a heat sealing machine, and is excellent in releasability (non-stickiness), slippage (friction properties), and flexibility (softness), and is therefore suitably used as a release material for a heat sealing machine. Furthermore, the release agent composition of the present invention is free from the concerns of environmental persistence and bioaccumulation, is a fluororesin-free material that is excellent in releasability, and is therefore suitably used as a release material for a heat sealing machine, etc.

[0009] The present invention is described in detail below, but is not limited thereto. [Fabric Sheet] The fabric sheet of the present invention has, on the surface and / or inside of (A) a woven or nonwoven fabric made of heat-resistant fibers, a cured product of a composition containing (B) an organopolysiloxane having a structure represented by average composition formula (I). (B) The cured product of the composition containing the organopolysiloxane having a structure represented by average composition formula (I) may further contain (C) a silicone powder. First, (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 the 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. Here, 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 fiber selected from glass fibers, carbon fibers, aramid resin fibers, polyimide resin fibers, phenolic resin fibers, and polyparaphenylenebenzobisoxazole fibers. As the woven fabrics or nonwoven fabrics 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 (B') an organopolysiloxane having a structure represented by average composition formula (I), which becomes the (B) cured product 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 of (B') has a structure represented by the following average composition formula (I).

[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 methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, and n-dodecyl groups. Specific examples of aryl groups having 6 to 10 carbon atoms include phenyl and naphthyl groups. 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 preferred, a methyl group, an ethyl group, or a phenyl group is more preferred, and a methyl group is even more preferred.

[0015] Above, R ３ , R ４ and R ５each 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, or an alkoxy or hydroxy group having 1 to 4 carbon atoms. Specific examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, and n-dodecyl. Specific examples of alkenyl groups having 2 to 8 carbon atoms include vinyl, allyl, 3-butenyl, 5-hexenyl, and 7-octenyl. Specific examples of aryl groups having 6 to 10 carbon atoms include phenyl and naphthyl. Specific examples of aralkyl groups having 7 to 10 carbon atoms include benzyl and phenylethyl. 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 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 preferred, a methyl group, an ethyl group, or a phenyl group is more preferred, and a methyl group is even more preferred.

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

[0017] a, b, c, d, e, and f are 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. a is a number that satisfies 0≦a<1, but from the viewpoint of the non-adhesiveness (releasability), frictional properties, and flexibility (flexibility) of the obtained sheet, 0≦a≦0.5 is preferred, and 0≦a≦0.2 is more preferred. b is a number that satisfies 0<b≦1, but from the viewpoint of the non-adhesiveness (releasability), frictional properties, and flexibility (flexibility) of the obtained sheet, 0.01≦b≦0.5 is preferred, and 0.01≦b≦0.3 is more preferred. c is a number that satisfies 0≦c<1, but from the viewpoint of the non-adhesiveness (releasability), frictional properties, and flexibility (flexibility) of the obtained sheet, 0≦c≦0.4 is preferred, and 0≦c≦0.3 is more preferred. d is a number satisfying 0<d≦1, but from the viewpoint of the non-adhesiveness (releasability), frictional properties, and flexibility (flexibility) of the obtained sheet, 0<d≦0.8 is preferred, and 0.1≦d≦0.6 is more preferred. e is a number satisfying 0<e≦1, but from the viewpoint of the non-adhesiveness (releasability), frictional properties, and flexibility (flexibility) of the obtained sheet, 0.1≦e≦0.8 is preferred, and 0.1≦c≦0.6 is more preferred. f is a number satisfying 0≦f<1, but from the viewpoint of the non-adhesiveness (releasability), frictional properties, and flexibility (flexibility) of the obtained sheet, 0≦f≦0.5 is preferred, and 0≦f≦0.2 is more preferred.

[0018] The organopolysiloxane (B') can be synthesized by a typical hydrolysis condensation reaction and hydrosilylation reaction. For example, it can be obtained by hydrosilylation reaction of an oligomer (c1) obtained by hydrolysis condensation of a monomer containing a silane compound having hydrolyzable groups such as an alkenyl group and an alkoxysilyl group with a linear organohydrogenpolysiloxane (a1) having an SiH group at one end and an alkoxysilyl group at the other end, and a linear organohydrogenpolysiloxane (b1) having SiH groups at both ends. By reacting (c1) with (b1), the film-forming ability and flexibility (pliability) of the resulting organopolysiloxane are improved. Furthermore, by reacting (a1) in addition to (b1), the reactivity (curability) of the resulting organopolysiloxane can be improved. An organic solvent may be used during the hydrolysis condensation. Specific examples of usable organic solvents include methanol, ethanol, propanol, acetone, methyl ethyl ketone, tetrahydrofuran, toluene, and xylene.

[0019] Furthermore, if a large amount of unreacted (a1) and (b1) remains in the reaction product, the SiH groups may decompose over time, generating 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). Therefore, the ratio of the total number of SiH groups contained in (a1) and (b1) to the number of alkenyl groups contained in the oligomer (c1) is preferably [number of alkenyl groups] / [number of SiH groups] = 1.1 to 10, more preferably 1.2 to 5. Specific examples of methods for producing organopolysiloxane (B') include the methods 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, and 100 to 2,000 mm ２ / s is more preferable, and 200 to 1,000 mm ２ / s is more preferable, and 300 to 800 mm ２ / s is most preferred. Furthermore, 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, or propylene glycol monomethyl ether acetate. (B') can also be used as an emulsion dispersed in water using a surfactant or the like. 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). Furthermore, the weight-average molecular weight (Mw) of (B') measured in terms of polystyrene standards by gel permeation chromatography (GPC) is preferably 1,000 to 50,000, more preferably 5,000 to 20,000.

[0021] Other Components in (B) Silicone Powder (C) The cured product (B) may further contain a silicone powder (C) in addition to the organopolysiloxane having the structure represented by the average composition formula (I) (B'). That is, the composition containing the organopolysiloxane having the structure represented by the average composition formula (I) (B'), which becomes the cured product (B), may contain a silicone powder (C). Conventionally known silicone powders can be used, and examples thereof include resin powders made of polymethylsilsesquioxane, polymethyl-phenylsilsesquioxane (copolymer), polyphenylsilsesquioxane, etc.; rubber powders which are cross-linked products of dimethylpolysiloxane; and composite powders in which the surface of a rubber powder is coated with a 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.), and DOWSIL TREFIL E-506S Silicone Powder and DOWSIL EP-9215 Cosmetic Powder (manufactured by Dow Chemical Japan, Ltd.). 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 powder and composite powder are preferred, and from the viewpoint of ease of availability, resin powder is 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 cannot be obtained in terms of releasability (non-stickiness) and slipperiness (friction properties), and if it 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 alkoxide 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 tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, tris(acetylacetonato)aluminum, tris(propionylacetonato)aluminum, dipropoxypropionylacetonatoaluminum, acetylacetonato-bis(propionylacetonato)aluminum, monoethylacetoacetate-bis(acetylacetonato)aluminum, acetylacetonatoaluminum-di-s-butylate, methylacetoacetatealuminum-di-s-butylate, di(methylacetoacetate)aluminum-mono-t-butylate, diacetonatoaluminum-di-s-butylate, diacetonatoaluminum-mono-t-butylate, diacetonatoaluminum-di-s-butylate, diacetonatoaluminum-di-t ... Examples of the 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 the metal ester compound 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-ethylhexylate), dibenzyltin di(2-ethylhexylate), 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. Note that commercially available titanium chelate compounds can also be used, and examples thereof include 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 blended is preferably 0.1 to 15 parts by mass, 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 addition of the catalyst will be too short. The catalyst may be used alone or in combination of two or more types.

[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 additives may be used alone or in combination of two or more, with the amounts of each additive selected from the appropriate amounts. The proportion of (B') relative to the total of all components in the composition containing (B') is preferably 50 to 100% by mass, more preferably 60 to 98% by mass, and even more preferably 70 to 97% by mass.

[0029] (B') an organopolysiloxane having a structure represented by average composition formula (I) and other optional ingredients are mixed in the above-mentioned amounts by a known method and cured to obtain (B) a cured product of a 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 section on the method for producing a fabric sheet.

[0030] [Method for manufacturing fabric sheet] The fabric sheet of the present invention can be manufactured 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 predetermined 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) is preferably 10 to 300 g / m ２ , more preferably 20 to 200 g / m ２ , more preferably 30 to 100 g / m ２ 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 , more preferably 30 to 100 g / m ２ It 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 heater of heat sealing machine] 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). This may be used as a release material for a 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) and (C) a silicone powder will be described. Specific examples of (B') and (C) contained in the release agent composition of the present invention include those described above for the fabric sheet. Furthermore, the release agent composition of the present invention may contain the above-mentioned catalyst and other additives in addition to (B') and (C). The 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 (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 other additives in the release agent composition is selected from appropriate amounts depending on the type of additive. The proportion of (B') in the entire mold release agent composition is preferably 50 to 99% by mass, more preferably 60 to 98% by mass, and even more preferably 70 to 97% by mass. The mold release agent composition of the present invention forms a cured film having mold releasability when applied to a mold in a resin molding process and cured, thereby providing a mold release agent that is durable for repeated use. Furthermore, because the cured film has flexibility (pliability), it conforms to thermal expansion and contraction, providing a mold release agent with crack resistance.

[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 Canon-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 using a GPC (gel permeation chromatography) device manufactured by Tosoh Corporation, toluene as a solvent, and an RI detector. The ratio of the constituent units of (B) organopolysiloxane was determined using a 300 MHz-NMR measurement device manufactured by JEOL Ltd. １ H-NMR and ２９The vinyl group content (mol / 100 g, hereinafter referred to as vinyl value) was determined by reacting each product with Hanus's solution, reacting it with an aqueous potassium iodide solution, and titrating the resulting iodine with sodium thiosulfate.

[0038] [Explanation of each component] (A) Woven or nonwoven fabric made of heat-resistant fibers Commercially available glass cloth (plain weave, 50 g / m ２ An ultra-thin, dense plain woven micro glass cloth (#50) with a thickness of 0.045 mm and 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: 740 g (1.54 mol) of methyltrimethoxysilane, 160 g (0.27 mol) of vinylmethyldimethoxysilane, and 0.28 g of maleic anhydride were added to a 2 L three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer. 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. 6 g of cation exchange resin (Lewatit K2629, manufactured by LANXESS) was then added, and the reaction was carried out for another 3 hours at 70°C. The resulting reaction solution was distilled under atmospheric pressure, and after no more distillate was produced, it was heated at 105°C for 3 hours. Finally, the distillate was removed by distillation under reduced pressure (90°C, 1.3 kPa), yielding an organopolysiloxane compound (R1: yield 580 g). The resulting organopolysiloxane compound (R1) was a colorless, transparent liquid with a kinematic viscosity of 66 mm ２ 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 added to a 500 mL three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and mixed. At this time, 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 mol relative to the Si—H groups, and the reaction was carried out at 80°C for 3 hours. The fraction was then removed by distillation under reduced pressure (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 The structural unit ratios of the organopolysiloxane compound (R2) in formula (I) were a = 0, b = 0.01, c = 0, d = 0.85, e = 0.14, f = 0, m = 39, n = 2, R２ = methyl group, R ３ = methyl group, R ４ = methyl group and vinyl group.

[0044] Synthesis Example 3 230 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) were added to a 500 mL three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and mixed. At this time, 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 mol relative to the Si—H groups, and the reaction was carried out at 80° C. for 3 hours. Thereafter, the fraction was removed by distillation under reduced pressure (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 The structural unit ratios of the organopolysiloxane compound (R3) in formula (I) were 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 group and vinyl group.

[0045] [Synthesis Example 4] 221 g (1.63 mol) of methyltrimethoxysilane, 156 g (0.79 mol) of phenyltrimethoxysilane, 40 g of isopropyl alcohol, and 182 g of xylene were added to a 2 L three-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer. 12 g of methanesulfonic acid and 121 g of water were added while stirring at 15 ° C., and the reaction was carried out at 70 ° C. for 3 hours. After cooling the mixture in the flask to below 50 ° C., 12 g of sodium bicarbonate was added to neutralize it, and 280 g of xylene was added, followed by atmospheric distillation (80 ° C.) to remove by-product methanol and other fractions. The resulting solution was washed with water to remove the neutralization salt, and then atmospheric distillation (120 ° C.) and reduced pressure distillation (70 ° C., 1.3 kPa) were performed 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 an Mw of 8,000. The organopolysiloxane compound (R4) was also 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 1,155 g of 70°C warm water, and 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 thereto over 90 minutes, followed by polymerization at 70°C for 30 minutes. After cooling the mixture in the flask to below 50°C, the water in the lower layer 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 an Mw of 6,500. The organopolysiloxane compound (R5) was also represented by the following average composition formula: [(Me)SiO ３／２ ] ｄ１ [(Ph)SiO ３／２ ] ｄ２ [(Me) ２ SiO ２／２ ] ｅ１ [(Ph) ２ SiO 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 a curing catalyst D-20 to 20 g of an organopolysiloxane compound (R2) and further mixing. The coating liquid thus obtained had a deposition amount of about 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] 19 g of organopolysiloxane compound (R2) and 1 g of KMP-590 were mixed, and 2 g of a curing catalyst D-20 was added and further mixed to prepare a coating liquid. The coating liquid obtained had a deposition amount of about 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 liquid 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 then adding 2 g of a curing catalyst D-20 and mixing. The coating liquid thus obtained had a deposition amount of about 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 liquid was prepared by mixing 26.7 g of a 60% xylene solution of organopolysiloxane compound (R5) (16 g of R5) and 4 g of KMP-590, and then adding 2 g of a curing catalyst D-20 and mixing. The coating liquid thus obtained had a deposition amount of about 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 evaluation.

[0053] [Evaluation Items and Methods] Polyethylene (PE) Releasability A piece of polyethylene sheet (1 cm wide strip) was sandwiched between two fabric sheets (2 cm wide strips) and pressed with an iron at 200°C for 3 minutes to prepare a test piece. Thereafter, the peel force when one of the fabric sheets was peeled off in a 180° direction was measured, and the PE releasability was evaluated according to the following criteria: ◎: Less than 0.1 N ○: 0.1 to 0.2 N △: 0.2 to 0.3 N ×: 0.3 to 0.4 N XX: More than 0.4 N

[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 0.4 N ◯: 0.4 to 0.6 N △: 0.6 to 0.8 N ×: 0.8 to 1.0 N xx: More than 1.0 N

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

[0056]

[0057]

[0058]

[0059] As shown in Tables 1 and 2, the fabric sheets F1 to F11 of Examples 1 to 11 were found to have good PE releasability and slipperiness, and to have excellent flexibility with no breaks or cracks when bent. On the other hand, as shown in Table 3, the fabric sheets F12 and F13 of Comparative Examples 1 and 2 were found to have poor PE releasability, slipperiness, and flexibility. The commercially available fluororesin fabric sheet of Comparative Example 3 was found to have good PE releasability, slipperiness, and flexibility, but had issues due to the fluororesin content.

Claims

1. (A) A fabric sheet having, 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): (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 an integer 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) silicone powder.

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) 1m ２ The amount of (B) per ２ The fabric sheet according to claim 1, 6. 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') Organopolysiloxane having a structure represented by the following average composition formula (I): (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 an integer of 1 to 3; R ３ , R ４ and R ５ each independently represent 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.

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