JP5683848B2 - Curable organopolysiloxane composition, sheet-like article provided with a cured layer comprising the composition, and method for producing the same - Google Patents

Description

The present invention is a cured layer characterized in that even when a thick coating is applied to a substrate, an increase in the dynamic friction coefficient of the cured layer is suppressed as compared with a thin coating, and the speed dependency of the dynamic friction coefficient is small. Relates to a curable organopolysiloxane composition capable of forming More specifically, the curable organopoly which is easy to handle, can form a cured layer on the surface of the substrate, and can provide good peelability to an adhesive substance and smooth sliding of the cured layer. The present invention relates to a siloxane composition, and relates to a sheet-like substrate provided with a cured layer obtained by curing the composition, in particular, a surface protective sheet and a laminate comprising the sheet-like substrate. Furthermore, this invention relates to the manufacturing method of these sheet-like base materials and a surface protection sheet.

A method of imparting peelability to an adhesive substance by forming a cured layer of an organopolysiloxane composition on the surface of a substrate such as various papers, laminated papers, synthetic films, and metal foils is well known. In this case, as a method for forming a peelable cured film, an addition reaction type organopolysiloxane in which an organopolysiloxane having an unsaturated hydrocarbon group and an organohydrogenpolysiloxane are subjected to an addition reaction in the presence of a hydrosilylation reaction catalyst. Compositions (see, for example, Patent Document 1) are widely used, and in recent years, solvent-free peelable cured film-forming organopolysiloxane compositions have been demanded for a wide range of applications in consideration of safety and the environment. .

However, the conventional solvent-free peelable cured film-forming organopolysiloxane composition has a low viscosity of about 50 to 1000 cs, and does not contain a high-viscosity organopolysiloxane. Although it has excellent processability, there is a disadvantage in that the formed cured film is poorly slidable and its use is limited. In order to solve this problem, a composition in which a high-viscosity and low-reactivity organopolysiloxane is added to a composition constituting a cured film is known (see Patent Documents 2 to 4). In addition, the inventors have a viscosity at 25 ° C. of 20 to 300 mPa · s, (A) an organopolysiloxane having an alkenyl group and a silicon atom-bonded phenyl group, and (B) a viscosity of 100,000 mPa · s or more. A solvent-free peelable cured film-forming organopolysiloxane composition containing an organopolysiloxane has been proposed (see Patent Document 5).

On the other hand, it is known that organopolysiloxanes containing higher alkenyl groups such as hexenyl groups can be used as the main ingredients of organopolysiloxane compositions that cure by addition reactions, improving low-temperature curing properties and release properties for adhesive substances. It is known that this can be done (see Patent Documents 6 to 9). Further, Patent Document 10 discloses a curable coating composition containing 0.1 to 20% by weight of a higher alkenyl functional organopolysiloxane gum. It is described that a composition is obtained that has a stable peelability and a low coefficient of friction coating.

However, in these documents, an organopolysiloxane having a low viscosity and a higher alkenyl group content in the range of 1.0 to 5.0% by mass is used as a main agent, and a high viscosity organopolysiloxane, in particular, There is no disclosure of a curable organopolysiloxane composition to which an organopolysiloxane gum having vinyl groups only at the molecular chain ends is added. Furthermore, these documents do not describe or suggest any combination of two or more organopolysiloxanes having low viscosity and different content ranges of higher alkenyl groups.

Japanese Patent Laid-Open No. 47-32072 Japanese Patent Laid-Open No. 61-159480 JP 2006-206884 A JP 2008-169322 A International Publication WO2006 / 070947 Japanese Patent Laid-Open No. 02-145650 Japanese Patent Laid-Open No. 04-020570 Japanese Patent Laid-Open No. 05-171047 Japanese Patent Laid-Open No. 06-049413 JP-T 09-507523

The present invention has been made to solve the above-mentioned problems, is easy to handle, can form a cured layer on the surface of a substrate, has good releasability from an adhesive substance, and smooth sliding of the cured layer. It is intended to provide a curable organopolysiloxane composition capable of imparting properties.

Furthermore, the inventors have discovered a new technical problem to be solved by the present invention. The cured layer made of a known curable organopolysiloxane composition can be appropriately selected depending on the use of the sheet-like substrate provided with the cured layer, and the amount of less than 1.0 g / m ₂ can be selected. It may be necessary to form a hardened layer by thickly applying an amount of 1.0 to 10.0 g / m ² on the substrate, as well as a thin coating on top. However, as the thickness of the hardened layer increases, the dynamic friction coefficient of the hardened layer increases accordingly, and the slipping property of the hardened layer is impaired. Such a problem is prominent in applications in which both the peeling property and the adhesion property of the cured layer are important, such as an optical display and a protective film on a glass surface. Furthermore, the inventors tend to increase the peel strength of the hardened layer formed thick on the substrate, particularly when peeled at a high speed of 100 mm / min or more as compared to when peeled at a low speed. I found a significant problem.

Therefore, the present invention is characterized in that the increase in the dynamic friction coefficient of the cured layer is suppressed and the speed dependency of the dynamic friction coefficient is small even when the substrate is applied thickly, compared to the case where the substrate is applied thinly. Provided is a curable organopolysiloxane composition capable of forming a cured layer, a sheet-like substrate provided with a cured layer obtained by curing the composition, particularly a surface protective sheet and a laminate comprising the sheet-like article. To do. Furthermore, this invention provides the manufacturing method of these sheet-like articles | goods and a surface protection sheet.

The purpose is (A) one or more types having a viscosity at 25 ° C. of 20 to 500 mPa · s and a content of higher alkenyl groups having 4 to 12 carbon atoms in the range of 1.0 to 5.0 mass%. 100 parts by mass of the organopolysiloxane, (B) A liquid or gum shape having a viscosity at 25 ° C. of 1,000,000 mPa · s or more, and an alkenyl group content of 2 to 12 carbon atoms is 0.005 to 0 0.5 to 15 parts by mass of an organopolysiloxane in the range of 100% by mass, (C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms (Si—H) in one molecule (A) component, and (B) an amount in which the molar ratio of SiH groups in component (C) to alkenyl groups in component is 0.5 to 5 and (D) a platinum-based catalyst. It is achieved by polysiloxane composition.

That is, the purpose is
“[1] (A) One or more types having a viscosity at 25 ° C. of 20 to 500 mPa · s and a content of a higher alkenyl group having 4 to 12 carbon atoms in the range of 1.0 to 5.0 mass%. 100 parts by mass of an organopolysiloxane
(B) A liquid or gum shape having a viscosity at 25 ° C. of 1,000,000 mPa · s or more, and the content of alkenyl groups having 2 to 12 carbon atoms is in the range of 0.005 to 0.100 mass%. 0.5-15 parts by mass of organopolysiloxane,
(C) Organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms (Si-H) in one molecule (A) and moles of SiH groups in component (C) relative to alkenyl groups in component (B) A curable organopolysiloxane composition comprising an amount such that the ratio is 0.5 to 5 and (D) a platinum catalyst.
[2] Component (A) is (A1) an organopolysiloxane in which the content of a higher alkenyl group having 4 to 12 carbon atoms is in the range of 0.5 to 2.0% by mass, and (A2) 4 carbon atoms. A mixture of two or more types of organopolysiloxanes in which an organopolysiloxane having a content of -12 higher alkenyl groups in the range of 2.5 to 5.0% by mass is mixed at a mass ratio of 1/4 to 4/1. The curable organopolysiloxane composition according to [1].
[3] The curable organopolysiloxane composition according to [1] or [2], wherein the higher alkenyl group of component (A) is a hexenyl group.
[4] The curable organopolysiloxane composition according to [1], wherein the component (B) is dimethylpolysiloxane in which both ends of the molecular chain are blocked with dimethylvinylsiloxy groups.
[5] The curability according to any one of [1] to [4], which is a solventless type and has a viscosity of 100 to 5,000 mPa · s at 25 ° C. Organopolysiloxane composition.
[6] A curable organopolysiloxane composition is applied to a sheet-like substrate in an amount of 0.6 g / m ² or 1.6 g / m ^2, and each is applied at 130 ° C. for 30 seconds. In any one of [1] to [5], an increase rate (Δ)% of a dynamic friction coefficient obtained by the following formula is 10% or less for a cured layer obtained by heat curing. A curable organopolysiloxane composition.
Increase rate of dynamic friction coefficient (Δ)% = [{(Dynamic friction coefficient of hardened layer with coating amount of 1.6 g / m ² ) − (Dynamic friction coefficient of hardened layer with coating amount of 0.6 g / m ² )} / Coating Coefficient of dynamic friction of hardened layer with a work amount of 0.6 g / m ² ] × 100
[7] A sheet-like article having a cured layer obtained by heat-curing the curable organopolysiloxane composition according to any one of [1] to [6].
[8] The sheet-shaped substrate is coated with an amount such that the cured layer has a curable organopolysiloxane composition of 1.0 to 10.0 g / m ² according to any one of [1] to [6]. The sheet-like article according to [7], which is a cured layer that is processed and heat-cured.
[9] The sheet-like article according to [7] or [8], wherein the base material is polyethylene laminated paper or a plastic film.
[10] A surface protective sheet comprising the sheet-like article according to any one of [7] to [9].
[11] The curable organopolysiloxane composition according to any one of [1] to [6], wherein an amount of 1.0 to 10.0 g / m ² is applied to a sheet-like base material, followed by heat curing. The method for producing a sheet-like article according to [7] or [8], wherein a cured layer is formed by the method.
[12] A curable organopolysiloxane composition according to any one of [1] to [6] on a substantially transparent sheet-like substrate, in an amount of 1.0 to 10.0 g / m ^2. A method for producing a surface protective sheet, which is coated and a cured layer is formed by heat curing.
[13] (S1) A sheet having a cured layer formed by heat-curing the curable organopolysiloxane composition according to any one of [1] to [6] on at least one surface of a sheet-like substrate A laminate in which an adhesive sheet provided with an adhesive layer on at least one surface of an (SA) sheet-like substrate is attached to a shaped substrate so that the adhesive layer is in contact with the cured layer .
[14] (S1) A sheet comprising a cured layer formed by heat-curing the curable organopolysiloxane composition according to any one of [1] to [6] on at least one surface of a sheet-like substrate. (SR) A laminate comprising a release sheet provided with a release layer on at least one surface of a sheet-like base material, and bonded so that the release layer is in contact with the cured layer. Is achieved.

The curable organopolysiloxane composition of the present invention is characterized in that even when a thick coating is applied on a substrate, an increase in the dynamic friction coefficient is suppressed as compared with a thin coating, and its speed dependency is small. A cured layer can be formed. The cured layer exhibits good releasability and smooth sliding properties with respect to an adhesive substance. Furthermore, it is possible to provide a sheet-shaped article provided with a cured layer showing the above technical effect obtained by curing the composition, in particular, a surface protective sheet and a laminate comprising the sheet-shaped article. And a method for producing a surface protection sheet.

The curable organopolysiloxane composition according to the present invention has (A) a viscosity at 25 ° C. of 20 to 500 mPa · s, and a content of a higher alkenyl group having 4 to 12 carbon atoms of 1.0 to 5.0. One or more types of organopolysiloxane in the range of mass%, (B) Content of alkenyl group having 2 to 12 carbon atoms in a liquid or gum shape with a viscosity at 25 ° C. of 1,000,000 mPa · s or more Is in the range of 0.005 to 0.100 mass%, (C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms (Si—H) in one molecule, and (D) a platinum-based It is characterized by containing a catalyst. Hereinafter, each component of the curable organopolysiloxane composition, a sheet-like article and a laminate using the composition will be described in detail.

The component (A) has a viscosity at 25 ° C. of 20 to 500 mPa · s, and the content of the higher alkenyl group having 4 to 12 carbon atoms is in the range of 1.0 to 5.0 mass%. Organopolysiloxane. By using the above component (A) having a low viscosity and a high content of higher alkenyl groups such as hexenyl groups as a main agent, a cured layer having a high crosslinking density can be formed on the substrate surface, and The content of the alkenyl group is in the range of 0.005 to 0.100% by mass from the inside to the surface of the cured layer, and the bleedout of the component (B) having low reactivity is effectively promoted. As a result, even when the curable organopolysiloxane composition of the present invention is applied thickly on the substrate, the increase in the dynamic friction coefficient and the speed dependency according to the thickness of the cured layer are suppressed, and the adhesive material is excellent. Exhibits releasability and smooth slip. If the content of the higher alkenyl group is less than the lower limit, the dynamic friction coefficient increases as the obtained hardened layer becomes thick, and the dynamic friction coefficient of the hardened layer shows speed dependency, so the object of the present invention cannot be achieved. On the other hand, if the content of the higher alkenyl group exceeds the upper limit, bleeding out of the component (B) on the surface of the cured layer may be inhibited, and the technical effect of good peelability and smooth slipping may be impaired. .

In view of the technical effect of the present invention, the component (A) preferably has a content of higher alkenyl groups having 4 to 12 carbon atoms in the range of 1.5 to 4.0% by mass. The 4 to 12 higher alkenyl groups are particularly preferably hexenyl groups, and organopolysiloxanes having hexenyl groups at both molecular chain terminals and side chains as represented by the following structural formula are preferred. Furthermore, from the viewpoint of the technical effect of changing the dynamic friction coefficient according to the thickness of the hardened layer and suppressing its speed dependency, the component (A) contains (A1) the content of a higher alkenyl group having 4 to 12 carbon atoms. And an organopolysiloxane having a content of higher alkenyl groups having 4 to 12 carbon atoms in the range of 2.5 to 5.0% by mass. It is preferable that the mixture is a mixture of two or more kinds of organopolysiloxanes in which siloxane is mixed at a mass ratio of 1/4 to 4/1, more preferably 1/2 to 2/1. The content of the higher alkenyl group is preferably in the range of 1.5 to 4.0% by mass, and particularly preferably in the range of 2.0 to 3.5% by mass.

（式中、ｍ，ｎは各々正の数であり、ｍは分子中のヘキセニル基（−（ＣＨ_２）_４ＣＨ＝ＣＨ_２）の含有量が１．０〜５．０質量％の範囲となる数である。また、ｍ＋ｎは、２５℃における粘度が２０〜５００ｍＰａ・ｓとなる範囲の数である。）

(Wherein m and n are each a positive number, and m is a range in which the hexenyl group (— (CH ₂ ) ₄ CH═CH ₂ ) content in the molecule is 1.0 to 5.0% by mass) Moreover, m + n is a number in the range where the viscosity at 25 ° C. is 20 to 500 mPa · s.)

In particular, when emphasizing the technical effect of suppressing an increase in the dynamic friction coefficient (speed dependency) of the substrate-cured layer surface when measured at a high speed, the component (A) has a higher alkenyl group content. It is particularly a mixture of one or more organopolysiloxanes or a mixture of two or more organopolysiloxanes in the range of 2.0 to 5.0% by mass, more preferably in the range of 2.0 to 3.5% by mass. preferable.

The component (B) is an additive for imparting slipperiness to the surface of the cured layer, and more specifically, effective on the surface of the cured layer formed by curing at a high crosslinking density by using the component (A). It is a component that gives an appropriate dynamic friction coefficient to the surface of the cured layer by bleed-out to give good peelability and smooth slipperiness to the adhesive substance.

The component (B) has a liquid or gum shape with a viscosity at 25 ° C. of 1,000,000 mPa · s or more, and the content of alkenyl groups having 2 to 12 carbon atoms is 0.005 to 0.100 mass%. An organopolysiloxane in the range. Examples of organic groups bonded to silicon atoms other than alkenyl groups include alkyl groups such as methyl groups, ethyl groups, and propyl groups; aryl groups such as phenyl groups; 3,3,3-trifluoropropyl groups, and nonafluorohexyl groups. And a silanol group is exemplified.

In order to achieve the object of the present invention, the content of the alkenyl group having 2 to 12 carbon atoms in the component (B) is 0.005 to 0.100% by mass, preferably 0.010 to 0.050% by mass. % Is preferably a low-reactivity organopolysiloxane, more than 90% of organic groups bonded to silicon atoms other than alkenyl groups, more preferably all are non-reactive alkyl groups or aryl groups. It is preferable. When the content of the alkenyl group in the component (B) is less than the lower limit, there may be a problem in that the amount of silicone transferred to the substrate increases and the residual adhesive rate decreases, and the content of the alkenyl group exceeds the upper limit. The component (B) is incorporated into the cured layer by an addition reaction, and the effect of imparting slipperiness to the surface of the cured layer may be insufficient.

The component (B) may be in the form of a liquid or raw rubber (gum) having a viscosity at 25 ° C. of 1,000,000 mPa · s or more. In the case of a liquid, the viscosity is 10,000,000 mPa · s or more. It is preferable that Moreover, when (B) component is gum-like, the plasticity (plasticity measured with a plasticity meter according to the method prescribed in JIS K 6249: 1 kgf on a spherical sample of 4.2 g at 25 ° C. The value when the load is applied for 3 minutes is preferably in the range of 0.5 to 10.0 mm, particularly preferably in the range of 0.9 to 3.0 mm.

Specifically, the component (B) was blocked with the same or different group selected from the group consisting of an alkyl group, an alkenyl group, an aryl group, a haloalkyl group, or a silanol group whose molecular chain ends were bonded to a silicon atom. Examples thereof include polydimethylsiloxane, dimethylsiloxane / phenylmethylsiloxane copolymer, and dimethylsiloxane / diphenylsiloxane copolymer. As such component (B), a linear or branched dimethylpolysiloxane whose molecular chain end is blocked with the same or different group selected from the group consisting of trimethylsiloxy group, silanol group or vinyl group is particularly preferred. preferable. A mixture of polydimethylsiloxanes having different degrees of polymerization may be used.

Most preferably, the component (B) is polydimethylsiloxane in which both ends of the molecular chain are blocked with dimethylvinylsiloxy groups, and in particular, gum-like polydimethylsiloxane can be preferably used.

The curable organopolysiloxane composition of the present invention contains 0.5 to 15 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), particularly 1.0 to 5.0 parts by mass. Part. If the content of the component (B) is less than the lower limit, the surface of the cured film is insufficiently slipped. If the content exceeds the upper limit, the viscosity of the organopolysiloxane composition becomes too high, and the solvent-free type is used. In some cases, actual work such as coating and manufacturing may be hindered.

Component (C) is an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms (Si—H) in one molecule, and is a crosslinking agent. The component (C) preferably has at least 3 silicon-bonded hydrogen atoms in one molecule, and the bonding position is not particularly limited. It is preferable that it is 0.1-2.0 mass% of the whole siloxane composition, and it is more preferable that it is 0.5-1.8 mass%. Moreover, as an organic group couple | bonded with the silicon atom which (C) component contains other than a hydrogen atom, the alkyl group of a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group is illustrated, and is a methyl group Is preferred. In addition, examples of the molecular structure include straight chain, branched chain, and branched ring.

(C) The viscosity in 25 degreeC of a component is 1-1000 mPa * s, Preferably it is 5-500 mPa * s. When the viscosity at 25 ° C. is less than 1 mPa · s, the component (C) is easily volatilized from the organopolysiloxane composition, and when it exceeds 1,000 mPa · s, the curing time of the organopolysiloxane composition is This is because it becomes longer. Specific examples of such a component (C) include a trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, a dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, Examples thereof include trimethylsiloxy group-blocked methyl hydrogen polysiloxane, cyclic methyl hydrogen polysiloxane, and cyclic methyl hydrogen siloxane / dimethyl siloxane copolymer. In addition, 2 or more types of organohydrogen polysiloxane can be used together as (C) component.

More preferably, the component (C) is one or more organohydrogenpolysiloxanes represented by the following general formula (2), and the silicon atom bond contained in the components (A) and (B) A cured layer is formed by an addition reaction (hydrosilylation reaction) with an alkenyl group.

In the formula, R ¹ is an unsubstituted or substituted monovalent saturated hydrocarbon group, and examples thereof are the same as those described above. Moreover, p is a positive integer, q is an integer of 2 or more, and p and q satisfy the relationship of 10 ≦ (p + q) ≦ 200. If (p + q) is less than the lower limit, it may volatilize and not sufficiently cure depending on the curing conditions. Moreover, when the said upper limit is exceeded, a gel may produce | generate with bath aging. Furthermore, p and q preferably satisfy the relationship of 0.3 ≦ q / (p + q) ≦ 1. If q / (p + q) is less than the lower limit, curing of the curable organopolysiloxane composition according to the present invention may be insufficient.

The amount of component (C) is such that the molar ratio of SiH groups in component (C) to alkenyl groups in components (A) and (B) is 0.5 to 5, preferably It is the quantity which becomes 1-3. If the molar ratio is less than the lower limit, the curability is lowered, and if the upper limit is exceeded, the peel resistance increases, and practical peelability may not be obtained.

The component (D) is a platinum-based catalyst that promotes an addition reaction (hydrosilylation reaction) between a silicon atom-bonded alkenyl group and a silicon atom-bonded hydrogen atom present in the system. Specific examples of preferable platinum-based catalysts include chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid olefin complexes, chloroplatinic acid and ketones complexes, chloroplatinic acid and vinylsiloxane complexes, platinum tetrachloride, Fine platinum powder, alumina or silica supported on solid platinum, platinum black, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, methyl methacrylate resin containing these platinum-based catalysts, polycarbonate Examples thereof include platinum-based catalysts of thermoplastic organic resin powders such as resins, polystyrene resins and silicone resins. In particular, platinum such as chloroplatinic acid and divinyltetramethyldisiloxane complex, chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane complex, platinum divinyltetramethyldisiloxane complex, platinum tetramethyltetravinylcyclotetrasiloxane complex, etc. An alkenylsiloxane complex can be preferably used.

Component (D) may be added in a catalytic amount, and is usually 1 to 1,000 ppm in terms of platinum-based metal content of component (D) with respect to the total mass of the curable organopolysiloxane composition of the present invention. And preferably in the range of 5 to 500 ppm.

In addition to the above components, the curable organopolysiloxane composition of the present invention has (E) a hydrosilylation reaction in order to improve the storage stability by suppressing gelation and curing at room temperature and to make it thermosetting. It is preferable to contain an inhibitor. Examples of hydrosilylation reaction inhibitors include acetylene compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, and oxime compounds. Specifically, 2-methyl-3-butyn-2-ol, 3,5-dimethyl Alkyne alcohols such as -1-hexyn-3-ol, 3-methyl-1-penten-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol (ETCH); 3 -Methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 3-methyl-3-pentene-1- In, 3,5-dimethyl-3-hexen-1-yne and the like and enyne compounds; 1-ethynyl-1-trimethylsiloxycyclohexane, bi (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl- Illustrative are alkenyl siloxanes such as 1,3,5,7-tetrahexenylcyclotetrasiloxane. (E) The addition amount of the hydrosilylation reaction inhibitor is usually in the range of 0.001 to 5 parts by mass per 100 parts by mass of component (A), but the type of this component, the performance and content of the hydrosilylation reaction catalyst The amount may be appropriately selected according to the content of the higher alkenyl group in the component (A), the amount of silicon atom-bonded hydrogen atoms in the component (C), the desired pot life and the working environment.

The composition of the present invention comprises a component (A), a component (B), a component (C), a component (D) and optionally a component (E), and in particular, a solvent-free curable organopolysiloxane composition. Suitable for use as The composition of the present invention may further contain an alkenyl group-containing organopolysiloxane resin in order to reduce the peel strength of the cured layer with respect to the adhesive substance. Further, a thickener such as silica fine powder may be further blended in order to increase the viscosity of the coating solution. In particular, when used in a solvent-free type, the composition of the present invention is preferably in the range of 50 to 10,000 mPa · s in viscosity of the entire composition at 25 ° C. in terms of coating properties to a sheet-like substrate. The viscosity of the entire composition is more preferably 100 to 5,000 mPa · s.

On the other hand, the composition of the present invention can be dispersed in a known organic solvent for the purpose of thin coating. Organic solvents include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, octane and isoparaffin, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and isobutyl acetate, etc. Ester solvents, ether solvents such as diisopropyl ether, 1,4-dioxane, cyclic polysiloxanes having a polymerization degree of 3-6 such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, trichloroethylene, Examples of halogenated hydrocarbons such as perchloroethylene, trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene, methylpentafluorobenzene, and sheets of polyolefin and the like having low heat resistance In the case of thin coating on the substrate, it is preferable to use an ether solvent from the viewpoint of curability and swelling. In the case of thin coating, even if it is thickly coated on the substrate, the increase in the dynamic friction coefficient is suppressed compared to the case of thin coating, and the technical effect of the present invention that the speed dependency is small is sufficient. It may not be.

In addition to the above components, optional components can be added to the curable organopolysiloxane composition according to the present invention. For example, an adhesion promoter comprising an alkoxysilane compound such as 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; phenol, quinone, amine, phosphorus, phosphite, sulfur, Antioxidants such as thioethers; light stabilizers such as triazoles and benzophenones; flame retardants such as phosphate esters, halogens, phosphorus, and antimony; cationic surfactants, anionic surfactants, non One or more kinds of antistatic agents composed of ionic surfactants and the like; known additives such as heat-resistant agents, dyes and pigments can be added.

In particular, a sheet-like article having a cured layer made of the composition according to the present invention is applied to an optical component such as a liquid crystal panel, a plasma display, a polarizing plate and a retardation plate, or an electric / electronic device such as a printed wiring board, IC, transistor or capacitor. When used as a surface protective film for protecting the surface of a component, addition of an antistatic agent is preferred.

The composition of the present invention can be produced by simply uniformly mixing the components (A) to (D), the component (E) and other optional components. The order of addition of each component is not particularly limited, but when not immediately used after mixing, the component (A), the component (B) and the component (C) are mixed with the component (D) separately. It is preferable to store them in a mixture and mix them immediately before use. Moreover, in the composition consisting of the component (A) to the component (D) and the component (E), the amount of the component (E) is adjusted so that it is not crosslinked at room temperature, and is crosslinked and cured when heated. Compositions are also preferred.

The curable organopolysiloxane composition of the present invention as described above is applied on a sheet-like substrate uniformly, and conditions sufficient for the component (A) and the component (C) to crosslink by hydrosilylation reaction. When heated below, a sheet-like article having a cured layer excellent in slipperiness, transparency and adhesion to the sheet-like substrate can be produced on the surface of these sheet-like substrates. In addition, a cured layer obtained by curing the composition of the present invention is excellent in flexibility and air permeability, and has an advantage that air bubbles are less involved when it is attached to a non-planar object. For this reason, it can be used very suitably for applications in which both the peeling property of the cured layer and the adhesion property of the cured layer to the object to be protected are both important, such as an optical display and a glass surface protective film.

In particular, the curable organopolysiloxane composition of the present invention has a different coating amount on a sheet-like substrate (for example, polyethylene-laminated paper or polyethylene terephthalate film), specifically, an amount that is 0.6 g / m ² ( = Thin hardened layer) or 1.6 g / m ² (= thick hardened layer), and the rate of increase in the coefficient of dynamic friction for hardened layers obtained by heating and curing each at 130 ° C./30 seconds. A sheet-like substrate having an absolute value of (Δ)% of 15% or less can be obtained, and a hardened layer is formed in which an increase in the coefficient of dynamic friction is suppressed with respect to a change in coating amount. be able to. Moreover, the sheet-like base material provided with such a hardened layer can be obtained. Furthermore, according to the present invention, a sheet-like article having an increase in the dynamic friction coefficient of 5% or less can be obtained, and a sheet-like article having an increase in the dynamic friction coefficient of -15% to 3% can also be obtained. it can.

Here, the “dynamic friction coefficient of the hardened layer” in “increase rate (Δ)% of the dynamic friction coefficient” means the front and back surfaces of the sheet-like base material having the hardened layer on the surface one day after the formation of the hardened layer. In accordance with the standard of JIS P8147, using a measuring device such as Tensilon Tensile Tester, the dynamic friction coefficient is kinetic friction under the environment of load: 1000g, moving speed: 10mm / min, temperature 23 ° C, humidity 65%. It is a value determined by measuring the coefficient.

Further, the rate of increase (Δ)% in the dynamic friction coefficient is the same sheet-like article having a hardened layer coated in such an amount that the coating amount is 0.6 g / m ² or 1.6 g / m ^2. Is a value obtained by measuring the dynamic friction coefficient of each sample by the above method and determining the percentage increase in the dynamic friction coefficient of the cured layer according to the following formula.
Δ (%) = {(dynamic friction coefficient of the cured layer of coating weight 1.6 g / ^{m 2} - dynamic friction coefficient of the cured layer of coated amount 0.6g / ^{m 2)} / the coated amount 0.6 g / ^{m 2} Coefficient of dynamic friction of hardened layer} × 100

The sheet-like substrate is substantially flat, and a substrate having an appropriate width and thickness can be used without particular limitation depending on the use such as tape, film, etc. Specifically, Synthetic resin films, cloths, synthetic fibers, metal foils (aluminum foil, copper foil, etc.), glass fibers, and composite sheet-like substrates formed by laminating a plurality of these sheet-like substrates.

Examples of the synthetic resin film include synthetic resin films such as polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, polyvinyl chloride, and polyethylene terephthalate. Since the cured layer of the present invention is substantially transparent, when a highly transparent sheet-like substrate made of these synthetic resin films is selected as a substantially transparent sheet-like substrate, excellent protection is provided. This is useful in that a film can be obtained.

Examples of paper include Japanese paper, synthetic paper, polyolefin laminated paper (particularly polyethylene laminated paper), cardboard paper, and clay coated paper.

Although the thickness of the sheet-like base material illustrated as mentioned above is not particularly limited, it is usually about 5 to 300 μm. Furthermore, in order to improve the adhesion between the sheet-like substrate and the cured layer, a support film that has been subjected to primer treatment, corona treatment, etching treatment, or plasma treatment may be used. Examples of primer compositions that can be used include condensation type silicone primer compositions containing polydiorganosiloxane having SiOH groups at the ends, polysiloxanes having SiH groups and / or polysiloxanes having alkoxy groups, and condensation reaction catalysts. And an addition-type silicone primer composition containing a polydiorganopolysiloxane having an alkenyl group such as a vinyl group, a polysiloxane having a SiH group, and an addition reaction catalyst.

The surface opposite to the cured layer of the sheet-like substrate may be subjected to surface treatment such as treatment for preventing scratches, preventing stains, preventing fingerprint adhesion, antiglare, antireflection, and antistatic. Each of the surface treatments described above may be applied after coating the curable organopolysiloxane composition of the present invention on a sheet-like substrate, or the composition may be applied after the surface treatment.

Examples of the scratch prevention treatment (hard coat treatment) include treatment with a hard coat agent such as an acrylate, silicone, oxetane, inorganic or organic-inorganic hybrid.

Examples of the antifouling treatment include treatment with an antifouling treatment agent such as fluorine, silicone, ceramic, and photocatalyst.

Examples of the antireflection treatment include wet treatment by application of an antireflection agent such as fluorine or silicone, and dry treatment by vapor deposition or sputtering. Examples of the antistatic treatment include a treatment with an antistatic agent such as a surfactant, silicone, organic boron, conductive polymer, metal oxide, or vapor deposition metal.

The temperature for curing the curable organopolysiloxane composition of the present invention on the sheet-like substrate is generally 50 to 200 ° C, but 200 ° C if the heat resistance of the sheet-like substrate is good. That's all. The heating method is not particularly limited, and examples include heating in a hot air circulation oven, passing through a long heating furnace, and heat ray radiation using an infrared lamp or a halogen lamp. Moreover, you may make it harden | cure using heating and ultraviolet irradiation together. When the component (D) is a platinum alkenylsiloxane complex catalyst, even if the blending amount is 80 to 200 ppm in terms of platinum metal amount per total amount of the composition, in a short time of 1 to 40 seconds at 100 to 150 ° C. Further, a cured layer excellent in slipperiness, transparency and adhesion to a sheet-like substrate can be easily obtained.

On the other hand, for a sheet-like substrate such as polyolefin having low heat resistance, 50 ° C. to 100 ° C. is more preferable after coating the curable organopolysiloxane composition of the present invention on the sheet-like substrate such as polyolefin. It is preferable to heat at a low temperature of 50 to 80 ° C. In this case, the curing time can be stably cured from 30 seconds to several minutes (for example, 1 to 10 minutes).

As a method of applying the curable organopolysiloxane composition of the present invention to the surface of a sheet-like substrate, roll coating, reverse roll coating using dipping, spraying, gravure coating, offset coating, offset gravure, offset transfer roll coater, etc. Any known method for forming a cured layer such as a curtain coat, a comma coat, a Meyer bar using an air knife coat, a curtain flow coater or the like can be used without limitation.

The coating amount is set according to the use, but the amount of 0.1 to 200.0 g / m ² is generally used on the sheet-like substrate, and the curable organopolysiloxane of the present invention is used as a release layer. For the purpose of applying thinly, the amount of 0.1 to 1.0 g / m ² can be selected, and the purpose of applying thickly in applications where both releasability and adhesion are required, such as protective film applications Then, the quantity used as 1.0-10.0 g / m < ² > can be selected. Since the curable organopolysiloxane of the present invention is particularly excellent in slipping property when applied thickly, it is preferable to apply an amount of 1.0 to 10.0 g / m ^2, and 1.0 to 5 An amount of 0.0 g / m ² is particularly preferred.

The cured layer comprising the curable organopolysiloxane composition of the present invention has a function as a peelable cured layer. On the other hand, by thickly coating the composition, there is an advantage that it can be used as a slightly sticky adhesive layer while having excellent peeling properties equivalent to those when thinly coated. Hereinafter, the use of the composition of the present invention utilizing these characteristics will be described.

The composition of the present invention is useful for forming a cured layer having excellent surface slipperiness and releasability to adhesive substances, and particularly as a peelable cured film forming agent for process paper, asphalt wrapping paper, and various plastic films. It can be preferably used.

In particular, the cured layer made of the composition of the present invention is excellent in peeling properties with respect to other adhesive layers, and therefore, for laminated bodies such as process paper, adhesive material wrapping paper, adhesive tape, and adhesive labels, which are laminated bodies including an adhesive layer. It can be used as a release layer. Specifically, by using the curable organopolysiloxane composition of the present invention, (S1) curing obtained by heat-curing the curable organopolysiloxane composition of the present invention on at least one surface of the sheet-like substrate. A pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer (or adhesive layer) on at least one surface of a (SA) sheet-like base material is provided on the cured layer, with a sheet-like base material provided with a layer (release layer or release layer). A laminated body that is adhered and configured so that the pressure-sensitive adhesive layer contacts can be obtained.

The adhesive substances applied to the laminate are various adhesives, various adhesives, etc., and acrylic resin adhesives, rubber adhesives, silicone adhesives; acrylic resin adhesives, and synthetic rubber adhesives. And silicone adhesives, epoxy resin adhesives, and polyurethane adhesives. Moreover, sticky foods such as asphalt and straw, glue, and bird rice cake are exemplified.

On the other hand, the hardened layer made of the composition of the present invention can be used as a slightly sticky adhesive layer while having excellent peeling properties equivalent to those when thinly coated, particularly by coating the composition thickly. In particular, it is extremely useful in that it can be used as an adhesive layer such as a protective sheet or a re-peelable adhesive sheet. Such an adhesion layer has an advantage that it maintains stable adhesion for a long period of time after being applied to an object, and does not cause displacement or peeling of the application position, but has excellent removability after application for a long time. Further, there is an advantage that re-sticking is easy and deformation of the cured layer, whitening, adhesive residue and the like hardly occur when the protective sheet is used for a long period of time.

A protective sheet or re-peelable adhesive sheet comprising a hardened layer made of the composition of the present invention comprises a member such as a metal plate, a coated metal plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, or a glass plate. When transporting, processing or curing, it is used for purposes such as sticking to and protecting the surface of these members. Also, as a protective sheet used in the manufacturing process of various liquid crystal display panels (also called monitors or displays), the distribution process of polarizing plates, the manufacturing process and distribution process of resin members for various machines such as automobiles, food packaging, etc. It can be preferably used.

Similarly, since the protective sheet provided with the adhesion layer made of the cured layer of the present invention can be easily reapplied, it is suitable for the following various protective sheets for displays. The protective sheet of the present invention is used for the purpose of preventing scratches, dirt, fingerprint adhesion, antistatic, antireflection, peeping prevention, etc., in each scene during the production, distribution and use of these displays. Is done.

Specifically, the laminate as the surface protective sheet is obtained by using the curable organopolysiloxane composition of the present invention (S1) on at least one surface of the sheet-like substrate. (SR) a release sheet provided with a release layer on at least one surface of the sheet-like base material provided with a cured layer (release layer and adhesive layer) formed by heat-curing the siloxane composition, It can be obtained by a laminate formed by being stuck so that the release layer is in contact with the cured layer.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following examples, all parts are parts by mass, Hex is a hexenyl group, and Me is a methyl group. Viscosity and plasticity are values measured at 25 ° C. Further, the sliding property of the cured layer made of the curable organopolysiloxane composition was evaluated by measuring the dynamic friction coefficient by the following method.

[Formation of cured layer]
The curable organopolysiloxane composition is 0.6,1.0 in terms of siloxane on the surface of the substrate using a printability tester [manufactured by Akira Seisakusho; RI-2] according to the coating amount. Alternatively, an amount of 1.6 g / m ² was applied. The coated substrate was heat-treated at 130 ° C. for 30 seconds in a hot air circulating oven to form a cured layer on the surface of each substrate.

[Measurement of dynamic friction coefficient of polyethylene laminated paper]
One day after curing, measurement sample was obtained by overlaying the untreated back surface (paper substrate surface) of polyethylene-laminated paper having the cured layer obtained by the above method on the surface and the cured layer (surface, silicone cured layer). And using the Tensilon tensile tester (trademark: Tensilon RTC-1210, manufactured by Orientec), the load coefficient: 1000 g, the moving speed: Each moving speed was measured under the conditions of a temperature of 23 ° C. and a humidity of 65% under conditions of 10, 30, 100 mm / min. (Examples 1-3)

[Measurement of dynamic friction coefficient of polyethylene terephthalate film]
One day after curing, an untreated back surface (PET substrate surface) and a cured layer (surface, silicone cured layer) of a polyethylene terephthalate (PET) film (thickness 50 μm) having a cured layer obtained by the above method on the surface Using the Tensilon Tensile Tester (Trademark: Tensilon RTC-1210, manufactured by Orientec), the dynamic friction coefficient of the front and back of the PET film having the cured layer obtained by the above method was used as a measurement sample. Each moving speed was measured in an environment of a temperature of 23 ° C. and a humidity of 65% under the conditions of load: 1000 g, moving speed: 10, 30, 100 mm / min. (Examples 4 to 6)

[Increase rate of dynamic friction coefficient (Δ)%]
With respect to the sample coated with an amount of 0.6 g / m ² or 1.6 g / m ² , the dynamic friction coefficient (moving speed: measured value at 10 mm / min) is measured by the above method. The rate of increase (Δ)% in the dynamic friction coefficient of the cured layer was determined according to the following formula. For the moving speed of 30, 100 mm / min, the rate of increase in the dynamic friction coefficient was similarly calculated as a reference value (Tables 1 and 3).
Δ (%) = {(dynamic friction coefficient of the cured layer of coating weight 1.6 g / ^{m 2} - dynamic friction coefficient of the cured layer of coated amount 0.6g / ^{m 2)} / the coated amount 0.6 g / ^{m 2} Coefficient of dynamic friction of hardened layer} × 100

[Speed dependency of dynamic friction coefficient of hardened layer: (δ _S )%]
With respect to the cured layer having the same coating amount, the dynamic friction coefficient is measured by the above method under the conditions of moving speed: 10 mm / min and 100 mm / min, and the change (δ _S )% of the dynamic friction coefficient of the cured layer is expressed by the following formula: Sought according to.
δ _S (%) = {(Dynamic friction coefficient of hardened layer measured at a moving speed of 100 mm / min−Dynamic friction coefficient of hardened layer measured at a moving speed of 10 mm / min) / Measured at a moving speed of 10 mm / min. Coefficient of dynamic friction of cured layer} × 100

[Example 1]
(A1) polydimethylsiloxane having a hexenyl group at both molecular chain terminals and side chains (viscosity 220 mPa · s, hexenyl group content 1.15% by mass) 93.6 parts,
(B1) 3.0 parts of dimethylsiloxane raw rubber whose molecular chain end is blocked with a vinyl group having a plasticity of 1.4 mm, and (C1) trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 25 mPa · s. Silicon atom-bonded hydrogen atom content 1.6 mass%) 3.2 parts and (E) 0.2 part of (E) 1-ethynyl-1-cyclohexanol (ETCH) were mixed uniformly. In this mixture, (D) chloroplatinic acid / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6 mass%) is added in an amount such that the platinum metal amount becomes 100 ppm. Addition and blending were performed to obtain a solventless curable organopolysiloxane composition (= Composition 1) having a viscosity of 800 mPa · s. The molar ratio of silicon-bonded hydrogen atoms (Si—) H / Hex of the composition was 1.27. The obtained organopolysiloxane composition was coated with polyethylene laminated paper in the above-described method in amounts of 0.6, 1.0 and 1.6 g / m ² and cured to obtain dynamic friction of each cured layer. The coefficients were measured and the results are shown in Table 1.

[Example 2]
(A1) polydimethylsiloxane having a hexenyl group at both molecular chain terminals and side chains (viscosity 220 mPa · s, hexenyl group content 1.15% by mass) 46.8 parts,
(A2) Polydimethylsiloxane having a hexenyl group at both molecular chain terminals and side chains (viscosity 100 mPa · s, hexenyl group content 3.00 mass%) 44.5 parts,
(B1) 3.0 parts of dimethylsiloxane raw rubber whose molecular chain end is blocked with a vinyl group having a plasticity of 1.4 mm, and (C1) trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 25 mPa · s. 7.8 parts of silicon atom-bonded hydrogen atom content 1.6 mass%) (E) 1-ethynyl-1-cyclohexanol (ETCH) 0.2 part was uniformly mixed. In this mixture, (D) chloroplatinic acid / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6 mass%) is added in an amount such that the platinum metal amount becomes 100 ppm. Addition and blending were performed to obtain a solventless curable organopolysiloxane composition (= Composition 2) having a viscosity of 600 mPa · s. The composition had a silicon-bonded hydrogen atom (Si-) H / Hex molar ratio of 1.25. The obtained organopolysiloxane composition was coated with polyethylene laminated paper in the above-described method in amounts of 0.6, 1.0 and 1.6 g / m ² and cured to obtain dynamic friction of each cured layer. The coefficients were measured and the results are shown in Table 1.

[Example 3]
(A2) Polydimethylsiloxane having a hexenyl group at both molecular chain terminals and side chains (viscosity 100 mPa · s, hexenyl group content 3.00 mass%) 89.0 parts,
(B1) 3.0 parts of dimethylsiloxane raw rubber whose molecular chain end is blocked with a vinyl group having a plasticity of 1.4 mm, and (C1) trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 25 mPa · s. 7.8 parts of silicon atom-bonded hydrogen atom content 1.6 mass%) (E) 1-ethynyl-1-cyclohexanol (ETCH) 0.2 part was uniformly mixed. In this mixture, (D) chloroplatinic acid / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6 mass%) is added in an amount such that the platinum metal amount becomes 100 ppm. Addition and blending were performed to obtain a solventless curable organopolysiloxane composition (= Composition 3) having a viscosity of 300 mPa · s. The composition had a silicon-bonded hydrogen atom (Si-) H / Hex molar ratio of 1.25. The obtained organopolysiloxane composition was coated with polyethylene laminated paper in the above-described method in amounts of 0.6, 1.0 and 1.6 g / m ² and cured to obtain dynamic friction of each cured layer. The coefficients were measured and the results are shown in Table 1.

[Comparative Example 1]
Instead of component (A1) and component (A2), (CA1) polydimethylsiloxane having vinyl groups at both molecular chain terminals and side chains (viscosity 60 mPa · s, vinyl group content 1.60% by mass) 91.3 A solventless curable organopolysiloxane composition (= Comparative composition 1) was obtained in the same manner as in Example 2 except that the parts were used. The obtained organopolysiloxane composition was coated with polyethylene laminated paper in the above-described method in amounts of 0.6, 1.0 and 1.6 g / m ² and cured to obtain dynamic friction of each cured layer. The coefficients were measured and the results are shown in Table 1.

[Comparative Example 2]
Instead of component (A1) and component (A2), (CA2) polydimethylsiloxane having a hexenyl group at both molecular chain ends and side chains (viscosity 350 mPa · s, hexenyl group content 0.70 mass%) 91.3 A solvent-free curable organopolysiloxane composition (= Comparative composition 2) was obtained in the same manner as in Example 2 except that the parts were used. The obtained organopolysiloxane composition was coated with polyethylene laminated paper in the above-described method in amounts of 0.6, 1.0 and 1.6 g / m ² and cured to obtain dynamic friction of each cured layer. The coefficients were measured and the results are shown in Table 1.

[Comparative Example 3]
Instead of component (A1) and component (A2), (CA3) polydimethylsiloxane having hexenyl groups at both molecular chain ends and side chains (viscosity 100 mPa · s, hexenyl group content 8.00 mass%) 91.3 A solventless curable organopolysiloxane composition (= Comparative composition 1) was obtained in the same manner as in Example 2 except that the parts were used. The obtained organopolysiloxane composition was coated with polyethylene laminated paper in the above-described method in amounts of 0.6, 1.0 and 1.6 g / m ² and cured to obtain dynamic friction of each cured layer. The coefficients were measured and the results are shown in Table 1.

Moreover, about each cured layer of Example 2 and Comparative Examples 1-3, the peeling resistance value was measured by the method shown below. The obtained results are shown in Table 2.
[Peeling resistance value]
Acrylic solvent-type pressure-sensitive adhesive [manufactured by Toyo Ink Manufacturing Co., Ltd., trade name: Orbine BPS-5127] is uniformly applied to the cured layer formed by the above method using an applicator so that the solid content is 30 g / m2. And heated at a temperature of 70 ° C. for 2 minutes. Subsequently, a high-quality paper having a basis weight of 64 g / m 2 was bonded to the acrylic pressure-sensitive adhesive surface, and the obtained bonded paper was cut into a width of 5 cm to prepare a test piece. A load of 20 g / cm 2 was applied to the test piece and left in air at a temperature of 25 ° C. and a humidity of 60% for 24 hours. After that, using a tensile tester [Tensilon universal tester manufactured by A & D Co., Ltd.], the laminated paper was pulled under the conditions of an angle of 180 degrees and a peeling speed of 0.3 m / min, and the force required for peeling. (MN / 50 mm) was measured.

[Example 4]
The dynamic friction coefficient of each cured layer was measured in the same manner as in Example 1 except that a polyethylene terephthalate (PET) film was used instead of the polyethylene laminated paper, and the results are shown in Table 2.

[Example 5]
The dynamic friction coefficient of each cured layer was measured in the same manner as in Example 2 except that a polyethylene terephthalate (PET) film was used instead of the polyethylene laminated paper, and the results are shown in Table 2.

[Example 6]
The dynamic friction coefficient of each cured layer was measured in the same manner as in Example 3 except that a polyethylene terephthalate (PET) film was used instead of the polyethylene laminated paper, and the results are shown in Table 2.

When a polyethylene laminated paper is used as a base material, as shown in Table 1, for the present application composition, in particular, for composition 2 and composition 3, as 0.6, 1.0 and 1.6 g / m ² , Even when the coating thickness was changed, the increase in the dynamic friction coefficient of the hardened layer was suppressed within a range of 15% up and down, and the coating amount was 1.6 g / m ² (thick coating). However, the speed dependence of the dynamic friction coefficient was suppressed. In composition 3, even when the coating amount was 1.6 g / m ² (thick coating), the speed dependency of the dynamic friction coefficient was suppressed to 20% or less. On the other hand, each cured layer obtained by Comparative Examples 1 to 3, especially when peeled at a high speed of 30 mm / min or more, the dynamic friction coefficient of the cured layer exceeds the upper and lower 15% range, and the thickness to be applied. It changed greatly depending on. Similarly, for the cured layers of Comparative Examples 1 and 2, when the coating amount was 1.6 g / m ² (thick coating), the speed dependence of the dynamic friction coefficient of the cured layer showed a very large value. . Moreover, as shown in Table 2, all the hardened layers according to the comparative examples had large peeling resistance values.

When a polyethylene terephthalate film is used as a base material, as shown in Table 3, for the present application composition, in particular, for composition 2 and composition 3, as 0.6, 1.0 and 1.6 g / m ² , Even when the coating thickness was changed, an increase in the dynamic friction coefficient of the cured layer was suppressed.

Claims (13)

(A) One or more organopolysiloxanes having a viscosity at 25 ° C. of 20 to 500 mPa · s and a content of higher alkenyl groups having 4 to 12 carbon atoms in the range of 1.0 to 5.0 mass% 100 parts by mass,
(B) A liquid or gum shape having a viscosity at 25 ° C. of 1,000,000 mPa · s or more, and the content of alkenyl groups having 2 to 12 carbon atoms is in the range of 0.005 to 0.100 mass%. 0.5-15 parts by mass of organopolysiloxane,
(C) Organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms (Si-H) in one molecule (A) and moles of SiH groups in component (C) relative to alkenyl groups in component (B) A curable organopolysiloxane composition comprising an amount such that the ratio is 0.5 to 5 and (D) a platinum-based catalyst catalyst amount ,
Component (A) is (A1) an organopolysiloxane in which the content of a higher alkenyl group having 4 to 12 carbon atoms is in the range of 0.5 to 2.0 mass%, and (A2) having 4 to 12 carbon atoms. Curing , which is a mixture of two or more types of organopolysiloxane prepared by mixing organopolysiloxane having a higher alkenyl group content in the range of 2.5 to 5.0% by mass in a mass ratio of 1/4 to 4/1. Organopolysiloxane composition. The curable organopolysiloxane composition according to claim 1, wherein the higher alkenyl group of component (A) is a hexenyl group. The curable organopolysiloxane composition according to claim 1, wherein the component (B) is dimethylpolysiloxane having both ends of the molecular chain blocked with dimethylvinylsiloxy groups. The curable organopolysiloxane according to any one of claims 1 to 3 , wherein the curable organopolysiloxane is a solvent-free type and has a viscosity of 100 to 5,000 mPa · s at 25 ° C. Composition. A curable organopolysiloxane composition is applied to a sheet-like substrate in an amount of 0.6 g / m ² or 1.6 g / m ^2, and each is heated and cured at 130 ° C. for 30 seconds. The absolute value of the rate of increase (Δ)% in the coefficient of dynamic friction measured under the condition of a moving speed of 10 mm / min in accordance with the standard of JIS P8147 determined by the following formula is 10% or less. The curable organopolysiloxane composition according to any one of claims 1 to 4 , wherein
Increase rate of dynamic friction coefficient (Δ)% = [{(Dynamic friction coefficient of hardened layer with coating amount of 1.6 g / m ² ) − (Dynamic friction coefficient of hardened layer with coating amount of 0.6 g / m ² )} / Coating Coefficient of dynamic friction of hardened layer with a work amount of 0.6 g / m ² ] × 100 The sheet-like article which has a hardening layer formed by heat-hardening the curable organopolysiloxane composition of any one of Claims 1-5 . The hardened layer is applied to a sheet-like base material in an amount to become the curable organopolysiloxane composition 1.0 to 10.0 g / m ² according to any one of claims 1 to 5 , The sheet-like article according to claim 6 , which is a cured layer obtained by heat curing. The sheet-like article according to claim 6 or 7 , wherein the substrate is polyethylene laminated paper or a plastic film. It consists of a sheet-like article according to any one of claims 6-8, a surface protection sheet. The curable organopolysiloxane composition according to any one of claims 1 to 5 , wherein an amount of 1.0 to 10.0 g / m ² is applied to a sheet-like substrate, and the cured layer is formed by heat curing. The method for producing a sheet-like article according to claim 6 or 7 , wherein the sheet-shaped article is formed. It was applied in an amount of a curable organopolysiloxane composition 1.0 to 10.0 g / m ² according to any one of claims 1 to 5 on a transparency sheet-like base material, heating A method for producing a surface protective sheet, wherein a cured layer is formed by curing. (S1) A sheet-like substrate provided with a cured layer obtained by heat-curing the curable organopolysiloxane composition according to any one of claims 1 to 5 on at least one surface of the sheet-like substrate. (SA) A laminate comprising a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer on at least one surface of a sheet-like base material, and bonded so that the pressure-sensitive adhesive layer is in contact with the cured layer. (S1) A sheet-like substrate provided with a cured layer obtained by heat-curing the curable organopolysiloxane composition according to any one of claims 1 to 5 on at least one surface of the sheet-like substrate. (SR) A laminate in which a release sheet provided with a release layer on at least one surface of a sheet-like substrate is adhered so that the release layer is in contact with the cured layer.