JP7448486B2 - Curing reactive silicone pressure-sensitive adhesive compositions, cured products thereof, and their uses - Google Patents

Description

The present invention relates to a curing reactive silicone pressure-sensitive adhesive composition, a cured product thereof, and uses of the composition or the cured product.

Silicone materials have excellent properties such as heat resistance, chemical resistance, and electrical insulation properties, and are therefore used for various purposes. Silicone materials can be formed on a variety of substrates such as plastic, metal, glass, ceramic, paper, and wood, and have a wide range of uses, including daily necessities, medical supplies, and electronic products. Silicone materials are usually obtained by crosslinking organopolysiloxanes by hydrosilylation reactions. In particular, silicone pressure-sensitive adhesives that are crosslinked by heating using a hydrosilylation reaction are widely known. Since the hydrosilylation reaction proceeds even at room temperature, the entire system hardens or gels immediately after the addition of the hydrosilylation reaction catalyst, making handling difficult. For this reason, the hydrosilylation reaction catalyst is usually added to the liquid silicone composition just before the curing reaction and mixed uniformly, and the handling time (about several hours) is secured before the application process. Therefore, it is common to add a hydrosilylation reaction inhibitor to the composition in advance.

Patent Document 1 discloses that a curable silicone composition that is cured by a hydrosilylation reaction contains a phosphorus-containing hydrosilylation reaction retarder. However, Patent Document 1 neither describes nor suggests an adhesive composition.

Japanese Patent Application Publication No. 2007-308542

The present inventors discovered a new problem regarding silicone pressure-sensitive adhesives that are cured by a hydrosilylation reaction. That is, as mentioned above, the hydrosilylation reaction proceeds immediately after the addition of the catalyst, so the pot life of the composition after mixing is short, and it thickens and gels in a relatively short time even at room temperature, resulting in problems in handling workability. I am holding. In order to solve this problem, hydrosilylation reaction inhibitors have been used as described above, but there is still room for improvement in storage stability and handling workability obtained with conventional hydrosilylation reaction inhibitors. In addition, if the composition is cured in a partially thickened or gelled state, the crosslinking state of the composition tends to become uneven, and the final adhesive sheet may not be able to achieve its original adhesive properties. be.

Furthermore, in recent years, heat-melting silicone adhesive compositions and hot-melt molded products thereof have been used to fill irregularities and gaps on components and temporarily fix or permanently bond between components in the production of display devices, etc. However, such hot-melt adhesive sheets are non-flowable at 25°C, so unlike liquid silicone compositions, the hydrosilylation reaction catalyst is added at room temperature immediately before the curing reaction. Due to their nature, it is difficult to add them and uniformly disperse them into the composition using mechanical force. Therefore, in order to uniformly add the hydrosilylation reaction catalyst, a step of heating and melting the composition is required, but since the hydrosilylation reaction tends to proceed under heating conditions, the addition of the hydrosilylation reaction catalyst is difficult. The curing reaction of the entire composition tends to proceed during the heat-melting step, and the resulting heat-melt adhesive may not be able to maintain sufficient curing reactivity or moldability. Similar problems can also occur during molding, so even with molded heat-melt adhesive materials (for example, hot-melt adhesive sheets), the entire molded composition is completely cured and the curing reaction occurs after several days of storage. In some cases, the adhesive loses its properties and heat-melting properties, and cannot be used as a heat-meltable adhesive.

The present invention was made to solve the above problems, and even if it is liquid or non-fluid (including hot-melt properties) at room temperature and in the form of a single composition, its storage stability and handling work are improved. A curing reactive silicone pressure-sensitive adhesive composition that has excellent adhesive properties and moldability, and can be quickly cured by heating at high temperatures to obtain high adhesive strength, and which can obtain high adhesive strength by pressure bonding. The purpose is to provide a cured product thereof. A further object of the present invention is to provide a pressure-sensitive adhesive material to which the cured reactive silicone pressure-sensitive adhesive composition and its cured product are used. Similarly, an object of the present invention is to provide a laminate including a layer made of the cured reactive silicone pressure-sensitive adhesive composition or a cured product thereof, and a method for producing the laminate.

The purpose of the present invention is to
(A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule;
(B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule;
(C) a catalyst for hydrosilylation reaction, and
(D) a phosphorus-containing hydrosilylation reaction retarder,
including;
The content of component (B) is such that the silicon-bonded hydrogen atoms in component (B) are 0.5 mole or more per mole of all aliphatic unsaturated carbon-carbon bonds in the composition. This is achieved by a cured reactive silicone adhesive composition.

The phosphorus-containing hydrosilylation reaction retarder of component (D) is selected from the group consisting of phosphine compounds, phosphoric acid compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorous acid compounds, and phosphonous acid compounds. It is preferable that at least one kind is selected.

Component (D) is diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, tripropylphosphine, dicyclohexylphenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1 ,2-bis(diphenylphosphino)propane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 2,3-bis(diphenylphosphino)butane, 1,5 -Bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, bis(2-diphenylphosphinoethyl)phenylphosphinebis(diphenylphosphino)acetylene, 1,1-bis(diphenylphosphino) Ethylene, 1,2-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphino)ferrocene, 1,3-bis(dicyclohexylphosphino)propane, 1,2-bis(dimethylphosphino)ethane, Preferably, it is at least one phosphine compound selected from the group consisting of 1,2-bis(dimethylphosphino)benzene and 1,2-bis(diphenylphosphino)benzene.

The blending amount of component (D) is preferably in the range of 0.01 to 1,000 mol per 1 mol of metal atoms in component (C), and the amount of metal atoms in component (C) It is particularly preferable that the amount is 0.30 to 10 mol per mol.

The curable reactive silicone adhesive composition of the present invention has _{( E} ) a siloxane unit (M unit) and an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO _4/2 .

At least a part of component (E) has (Alk)R' ₂ SiO _1/2 in the molecule (wherein Alk independently represents an aliphatic unsaturated carbon-carbon bond-containing group, and R' each Curing reactivity containing at least a siloxane unit (M unit) represented by (independently representing an aliphatic unsaturated carbon-carbon bond-free group) and a siloxane unit (Q unit) represented by SiO _4/2 Organopolysiloxane resins are preferred.

The content of component (E) is preferably 0.1% by mass to 90% by mass of the total mass of component (A), component (B), and component (E).

The curable reactive silicone pressure-sensitive adhesive composition of the present invention may further contain (F) a solvent.

The curable reactive silicone adhesive composition of the present invention is preferably a one-component type or a single composition.

The cured reactive silicone adhesive composition of the present invention may be fluid as a whole at 25°C.

The above-mentioned cured reactive silicone adhesive composition was prepared by bonding a 50 μm thick adhesive layer obtained by curing the composition to a SUS plate, and tensile testing using a 180° peel test method according to JIS Z0237. It is preferable that the adhesive force measured at a speed of 300 mm/min is 0.1 gf/inch or more.

The cured reactive silicone pressure-sensitive adhesive composition of the present invention is non-flowable at 25°C as a whole and may have a softening point between 25°C and 150°C. Furthermore, the curing-reactive silicone pressure-sensitive adhesive composition of the present invention may have tackiness before the curing reaction.

The above-mentioned cured reactive silicone adhesive composition was prepared by bonding a 200 μm thick adhesive layer obtained by curing the composition to a SUS plate, and tensile testing using a 180° peel test method according to JIS Z0237. It is preferable that the adhesive force measured at a speed of 300 mm/min is 0.1 gf/inch or more.

The present invention uses the above-mentioned cured reactive silicone adhesive composition (preferably, the composition as a whole is non-flowable at 25°C and has a softening point between 25°C and 150°C), It also relates to at least a member, component, or sheet.

Here, non-flowability means not flowing under no load, and for example, the ring and ball method for hot melt adhesives specified in JIS K 6863-1994 "Softening point test method for hot melt adhesives". A state in which the softening point measured by the softening point test method according to the above is between 25°C and 150°C.

Similarly, the present invention provides a cured reactive silicone adhesive composition as described above (preferably, the composition as a whole is non-flowing at 25°C and has a softening point between 25°C and 150°C). ) also relates to a heat-meltable adhesive material.

The present invention also relates to a cured product of the above-mentioned curing reactive silicone pressure-sensitive adhesive composition.

The present invention also relates to a method for producing the cured product, which includes a step of applying or molding the above-mentioned curing reactive silicone pressure-sensitive adhesive composition at a temperature of less than 150°C, and then curing it by heating to 150°C or higher.

The present invention also relates to a pressure-sensitive adhesive material comprising a cured product of the above-mentioned curing reactive silicone pressure-sensitive adhesive composition.

The present invention also relates to a laminate comprising a layer or member made of the above-mentioned curing reactive silicone pressure-sensitive adhesive composition. Similarly, the present invention also relates to a laminate comprising a layer or member made of a cured product of the above-mentioned curing reactive silicone pressure-sensitive adhesive composition.

These laminates may include at least a part of a sheet-like member provided with a release layer. For example, a member, component, or sheet made of at least the above composition or a cured product thereof may be provided with a release layer. It may be a releasable laminate, which is disposed so as to face a sheet-like member and is peeled off from the release layer during use, using the above-mentioned composition or a cured product thereof as an adhesive material.

Further, these laminates may be at least one selected from a display device, an electronic component, or a solar cell module, and may be a display device such as a liquid crystal display or an organic EL display, for example. Moreover, the above-mentioned curing reactive silicone adhesive composition or its cured product may be used as a sealing material for electronic components such as LEDs and micro LEDs.

Suitably, the laminate of the present invention can be used in various articles together with at least one substrate. For example, the substrate may be an image display panel, a touch panel, an optical film, or a front or back protection sheet. In this case, the article is preferably a display device. It is further preferable that the display device is a liquid crystal display or an organic EL display. Further, the substrate may be a solar cell, a sealing material layer, or a front or back protection sheet. In this case, the article is preferably a solar cell module.

The invention also relates to methods of manufacturing these laminates. The laminate obtained by these manufacturing methods may be an intermediate material such as a releasable adhesive sheet, or may be a final product such as a display device provided with an adhesive layer or a precursor thereof.

The method for producing a laminate of the present invention may include the steps of heating the above-mentioned curing reactive silicone adhesive composition to 80° C. or higher to melt it, and molding or filling the melt.

The method for producing a laminate of the present invention includes, after or simultaneously with disposing the above-mentioned curing reactive silicone adhesive composition on at least one member or between members, heating the curing reactive silicone adhesive composition at 150°C. It may include a step of heating above.

The method for producing a laminate of the present invention includes a step of sandwiching and laminating the above-mentioned curing reactive silicone adhesive composition or cured product thereof, and a step of laminating the above-mentioned curing reactive silicone adhesive composition or cured product thereof. The method may include a step of crimping the member.

According to the present invention, it is liquid or non-flowable (including hot-melt properties) at room temperature, has excellent storage stability, handling workability, and moldability even in the form of a single composition, and It is possible to provide a curable reactive silicone pressure-sensitive adhesive composition that is rapidly cured by heating at high temperatures and can obtain high adhesive strength. Further, it is possible to provide a cured product thereof that can obtain high adhesive strength by pressure bonding. Furthermore, according to the present invention, it is possible to provide an adhesive material for which the curing reactive silicone pressure-sensitive adhesive composition and its cured product are used, and a laminate comprising a layer made of the curing reactive silicone pressure-sensitive adhesive composition or its cured product. and a method for manufacturing the laminate.

In particular, when the curable reactive silicone adhesive composition of the present invention is in the form of a liquid composition, even if it is a one-component composition containing a hydrosilylation catalyst, it will not thicken or gel in a short period of time. Since it can be stored for a long period of time, it has excellent storage stability and preservation stability, and is also excellent in handling workability. Further, even under storage conditions at a relatively high temperature of about 50° C., it does not thicken or gel in a short period of time, so it has excellent storage stability and handling workability under high temperature conditions.

By using the curing reactive silicone adhesive composition of the present invention, it is possible to design the above-mentioned one-component composition, but such a composition does not require mixing of components at the time of use, so it is easy for the user to use it. This method has the advantage that the step of preparing the composition described above is unnecessary, and problems of poor mixing and dispersion do not occur during the mixing. Furthermore, by using the above-mentioned one-component composition, it is possible to essentially avoid errors in the process caused by mistakes in the ratio of ingredients due to preparation mistakes, etc., so it can be used stably with a simple process. This has the advantage of greatly improving handling efficiency as a product, industrial productivity, and quality of the resulting adhesive.

The curing reactive silicone pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer with excellent adhesive strength by curing, and when peeling the pressure-sensitive adhesive layer from an adherend, the pressure-sensitive adhesive composition Cohesive failure of the adhesive layer is less likely to occur. Preferably, the pressure sensitive adhesive layer is interfacially releasable from the adherend.

Further, the cured reactive silicone pressure-sensitive adhesive composition of the present invention is non-flowable at 25°C, has a softening point between 25°C and 150°C, and may have heat-melting properties. In the composition of the present invention, the progress of the curing reaction is suppressed by the addition of a hydrosilylation catalyst or by heating and melting during molding of the composition. A meltable curing reactive silicone adhesive composition and a molded product thereof can be provided. Therefore, the cured reactive silicone pressure-sensitive adhesive composition of the present invention can be softened or flowed by heating. As a result, the cured reactive silicone pressure-sensitive adhesive composition of the present invention can satisfactorily follow the irregularities on a member in a molten state to fill in steps, and has excellent gap-filling properties. Further, since the curing reactive silicone pressure-sensitive adhesive composition of the present invention can be heat-melted, the molten fluid can be molded into a desired shape such as a sheet. Molded products such as sheets made of the curing reactive silicone adhesive composition before the curing reaction themselves have heat-melting properties, adhesive properties, and curing reactivity, so they can be applied to desired areas using adhesive strength. By disposing and heating and melting, the fluid may flow into the irregularities of the base material.

FIG. 1 is a sectional view showing a laminate according to an embodiment of the present invention. 1 is a flowchart showing a method for manufacturing a laminate according to an embodiment of the present invention. FIG. 2 is a conceptual diagram of a method for manufacturing a laminate including a heating and melting process. 1 is a cross-sectional view of an optical display of one embodiment of an article of the invention. FIG. 1 is a cross-sectional view of an optical display of one embodiment of an article of the invention. FIG. FIG. 3 is a cross-sectional view of an optical display of another embodiment of an article of the invention. FIG. 3 is an exploded perspective view of an optical display of another embodiment of an article of the present invention. FIG. 6 is a partial cross-sectional view showing an optical display of another embodiment of an article of the invention.

As a result of intensive studies, the present inventors found that (A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule; and (C) a hydrosilylation catalyst in combination under predetermined conditions, and (D) a phosphorus-containing hydrosilyl. By incorporating a curing reaction retarder, it is possible to provide a curing reactive silicone adhesive composition that does not thicken in a relatively short period of time even in the form of a single composition and has high storage stability. They discovered this and completed the present invention.

The cured reactive silicone pressure-sensitive adhesive composition of the present invention may be a liquid composition that has fluidity at 25°C, or is non-flowable at 25°C and has a softening point between 25°C and 150°C. It may be a hot-melt composition having the following properties. When designed as a hot-melt composition, the entire composition can be softened or flowed by heating. The softening or fluidizing temperature is preferably 50 to 150°C, more preferably 60 to 130°C, and even more preferably 80 to 120°C.

Each aspect of the present invention will be described in more detail below.

First, the curing reactive silicone pressure-sensitive adhesive composition according to the present invention will be explained. In addition, in this specification, "mass %" is synonymous with "weight %", and the reference|standard is the total mass (total weight) of the composition etc. of this invention, unless otherwise specified.

[Curing reactive silicone adhesive composition]
The cured reactive silicone adhesive composition of the present invention includes:
(A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule;
(B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule;
(C) a catalyst for hydrosilylation reaction, and
(D) a phosphorus-containing hydrosilylation reaction retarder,
including;
The content of component (B) is such that the silicon-bonded hydrogen atoms in component (B) are 0.5 mole or more per mole of all aliphatic unsaturated carbon-carbon bonds in the composition. Furthermore, the curable reactive silicone adhesive composition of the present invention has (E) a siloxane unit represented by R ₃ SiO _1/2 (wherein R independently represents a monovalent organic group) in the molecule. (M unit) and an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO _4/2 .

Component (A) Component (A) is one of the main components of the curing reactive silicone pressure-sensitive adhesive composition of the present invention. Component (A) may be a single organopolysiloxane or a mixture of two or more organopolysiloxanes.
By using the component (A), the cured reactive silicone pressure-sensitive adhesive composition of the present invention or its cured product has sufficient adhesive strength, and in its adhesive mode, does not exhibit cohesive failure when peeled from the adherend. It is also possible to form an adhesive layer that is less likely to cause. Note that if permanent adhesion to an adherend is required, a composition with high adhesive strength that causes cohesive failure of the adhesive layer upon peeling can be designed.

Component (A) is a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule. In particular, it is preferable that the degree of siloxane polymerization is 80 or more. If the degree of polymerization is below the above range, it will be difficult to obtain adhesive strength.

The aliphatic unsaturated carbon-carbon bond-containing group is preferably an alkenyl group, alkenyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group as described above. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. Vinyl groups are particularly preferred. Further, some of these groups may be substituted with halogen atoms or the like.

When the component (B) is linear, the aliphatic unsaturated carbon-carbon bond-containing group may be present at either the end of the molecular chain, the side chain of the molecular chain, or both. good.

Preferably, the aliphatic unsaturated carbon-carbon bond-containing group is bonded to a silicon atom.

The content of the aliphatic unsaturated carbon-carbon bond-containing group is preferably 0.001 to 10% by weight, more preferably 0.005 to 5% by weight, based on the weight of component (A).

Component (A) may have an aliphatic unsaturated carbon-carbon bond-free group in addition to the aliphatic unsaturated carbon-carbon bond-containing group. The aliphatic unsaturated carbon-carbon bond-free group is preferably an alkyl group, an aryl group, or an aralkyl group as described above. Examples of the alkyl group include methyl, ethyl, propyl, pentyl, hexyl, octyl, and cycloalkyl groups such as cyclohexyl and cycloheptyl. Examples of the aryl group include phenyl group, tolyl group, xylyl group, and the like. Examples of the aralkyl group include benzyl group, α-methylstyryl group, and 2-phenylethyl group. The aliphatic unsaturated carbon-carbon bond-free group is more preferably an alkyl group, particularly preferably a methyl group. Further, some of these groups may be substituted with halogen atoms or the like.

As component (A), one having the following average compositional formula (1) is preferable.

R ¹ _a R ² _b SiO _(4-ab)/2 (1)

In the average compositional formula (1), R ¹ is an alkenyl group having 2 to 12 carbon atoms. Specifically, vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, and dodecenyl groups are mentioned, and among these, vinyl groups and allyl groups Or a hexenyl group is preferred. R ² is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group, and an alkoxy group having no aliphatic unsaturated bond. In the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, some of its hydrogen atoms may be substituted with halogen atoms or hydroxyl groups. Examples of monovalent saturated hydrocarbon groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, Alkyl groups such as dodecyl group, phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, aryl group such as pyrenyl group, benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group aralkyl groups such as phenanthrylethyl and pyrenylethyl groups, and hydrogen atoms of these aryl or aralkyl groups to alkyl groups such as methyl and ethyl groups; alkoxy groups such as methoxy and ethoxy groups; chlorine atoms , a group substituted with a halogen atom such as a bromine atom.

a and b are numbers that satisfy the following conditions: 1≦a+b≦3 and 0.0001≦a/(a+b)≦0.33, and preferably satisfy the following conditions: 1.5≦a+b≦2.5 and The number satisfies 0.0002≦a/(a+b)≦0.2. This is because when a+b is 1 or more, the flexibility of the cured product becomes high, while when a+b is 3 or less, the mechanical strength of the cured product becomes high. Further, if a/(a+b) is 0.0001 or more, the mechanical strength of the cured product will be high, while if it is 0.33 or less, the flexibility of the cured product will be high.

As such component (A), the general formula:
R ⁶ ₃ SiO(R ⁶ ₂ SiO) _m1 SiR ⁶ ₃
A linear organopolysiloxane represented by is preferred. However, component (A) may include a branched siloxane unit represented by R ⁶ SiO _3/2 or SiO _4/2 in part, and may be a branched organopolysiloxane.

In the formula, each R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group, exemplified by the monovalent unsaturated hydrocarbon group and monovalent saturated hydrocarbon group mentioned above. However, at least two R ⁶ in one molecule are monovalent unsaturated hydrocarbon groups, preferably alkenyl groups, and more preferably vinyl groups. The property of the organopolysiloxane having the average composition formula (1) at room temperature may be oil-like or rubber-like, and the viscosity of the component (A) is 50 mPa·s or more, particularly 100 mPa·s or more at 25°C. It is preferable.

Component (B) Component (B) is one of the main components of the curing reactive silicone adhesive composition of the present invention, and functions as a crosslinking agent. Component (B) may be a single organohydrogenpolysiloxane or a mixture of two or more organohydrogenpolysiloxanes.

Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. When component (A) or component (E) (described below) has an aliphatic unsaturated carbon-carbon bond-containing group, component (B) is the aliphatic unsaturated carbon-containing group of component (A) and component (E). Contains a hydrosilyl group (-SiH) that attaches to a carbon bond.

As component (B), an organopolysiloxane having the following average composition formula (2) is preferable.

H _c R ³ _d SiO _(4-c-d)/2 (2)

In the average compositional formula (2), R ³ is a group selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group. In the monovalent hydrocarbon group having 1 to 12 carbon atoms, some of its hydrogen atoms may be substituted with halogen atoms or hydroxyl groups. Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and undecyl group. , alkyl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenyl group. Aralkyl groups such as ethyl group, phenanthrylethyl group, pyrenylethyl group, and the hydrogen atom of these aryl or aralkyl groups can be replaced with methyl group, alkyl group such as ethyl group; alkoxy group such as methoxy group, ethoxy group; chlorine Examples include groups substituted with atoms and halogen atoms such as bromine atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentanoxy, hexanoxy, octanoxy, and the like.

c and d are numbers that satisfy the following conditions: 1≦c+d≦3 and 0.002≦c/(c+d)≦0.5, preferably, the following conditions: 1.5≦c+d≦2.5 and The number satisfies 0.01≦c/(c+d)≦0.5. This is because when c+d is 1 or more, the flexibility of the cured product becomes high, whereas when it is 3 or less, the mechanical strength of the cured product becomes high. Further, if c/(c+d) is 1.5 or more, the mechanical strength of the cured product will be high, while if it is 2.5 or less, the flexibility of the cured product will be high.

The viscosity of the organopolysiloxane having the average compositional formula (2) is not limited, but it is preferably within the range of 0.5 to 10,000 mPa·s, particularly 1 to 1,000 mPa·s at 25°C. It is preferably within the range of s.

Examples of the organopolysiloxane having the average composition formula (2) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris(dimethylhydrogensiloxy)methylsilane. , tris(dimethylhydrogensiloxy)phenylsilane, 1-(3-glycidoxypropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-di(3-glycidoxypropyl)- 1,3,5,7-tetramethylcyclotetrasiloxane, 1-(3-glycidoxypropyl)-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, both ends of the molecular chain Trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain terminals blocked with trimethylsiloxy groups dimethylsiloxane/methylhydrogensiloxane copolymer, molecular chain terminals blocked with dimethylhydrogensiloxy group dimethylpolysiloxane, molecular chain terminals blocked with dimethylhydrogen Siloxy group-blocked dimethylsiloxane/methylhydrogensiloxane copolymer, both molecular chain ends blocked with trimethylsiloxy groups, methylhydrogensiloxane/diphenylsiloxane copolymer, both molecular chain ends blocked with trimethylsiloxy groups, methylhydrogensiloxane/diphenylsiloxane/dimethyl Siloxane copolymer, hydrolyzed condensate of trimethoxysilane, copolymer consisting of (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units and SiO ₄ Copolymers consisting of _/2 units and (C ₆ H ₅ )SiO _3/2 units, and mixtures of two or more thereof are exemplified.

The following organopolysiloxanes are further exemplified as the organopolysiloxane having the average compositional formula (2). In addition, in the formula, Me and Ph represent a methyl group and a phenyl group, respectively, m2 is an integer of 1 to 100, n2 is an integer of 1 to 50, and b2, c2, d2, and e2 are each positive. However, the total of b2, c2, d2, and e2 in one molecule is 1.
_HMe2SiO ( _{Ph2SiO ) m2SiMe2H}
HMePhSiO(Ph ₂ SiO) _m2 SiMePhH
HMePhSiO(Ph ₂ SiO) _m2 (MePhSiO) _n2 SiMePhH
HMePhSiO(Ph ₂ SiO) _m2 (Me ₂ SiO) _n2 SiMePhH
(HMe ₂ SiO _1/2 ) _b2 (PhSiO _3/2 ) _c2
(HMePhSiO _1/2 ) _b2 (PhSiO _3/2 ) _c2
(HMePhSiO _1/2 ) _b2 (HMe ₂ SiO _1/2 ) _c2 (PhSiO _3/2 ) _d2
(HMe ₂ SiO _1/2 ) _b2 (Ph ₂ SiO _2/2 ) _c2 (PhSiO _3/2 ) _d2
(HMePhSiO _1/2 ) _b2 (Ph ₂ SiO _2/2 ) _c2 (PhSiO _3/2 ) _d2
(HMePhSiO _1/2 ) _b2 (HMe ₂ SiO _1/2 ) _c2 (Ph ₂ SiO _2/2 ) _d2 (PhSiO _3/2 ) _e2

Component (B) is preferably an organohydrogenpolysiloxane represented by the following average composition formula (3).

(HR ⁴ ₂ SiO _1/2 ) _e (R ⁴ ₃ SiO _1/2 ) _f (HR ⁴ SiO _2/2 ) _g (R ⁴ ₂ SiO _2/2 ) _h (HSiO _3/2 ) _i (R ⁴ SiO _3/2 ) _j (SiO _4/2 ) _k (R ⁵ O _1/2 ) _l (3)

In the average compositional formula (3), R ⁴ is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group, and an alkoxy group having no aliphatic unsaturated bond. The monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, the hydroxyl group, and the alkoxy group are the same as described above. R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, and hexyl group. e, f, g, h, i, j, k and l are under the following conditions: e+f+g+h+i+j+k=1, 0≦l≦0.1, 0.01≦e+g+i≦0.2, 0≦e≦0.6, The numbers satisfy 0≦g≦0.6, 0≦i≦0.4, 0.01≦e+f≦0.8, 0.01≦g+h≦0.8, and 0≦i+j≦0.6.

In addition, the above-mentioned "HR ⁴ ₂ SiO _1/2 ", "R ⁴ ₃ SiO _1/2 ", "HR ⁴ SiO _2/2 ", "R ⁴ ₂ SiO _2/2 ", "HSiO _3/2 ", The constituent units of "R ⁴ SiO _3/2 " and "SiO _4/2 " are organohydrogenpolysiloxane units called MH units, M units, DH units, D units, TH units, T units, and Q units, respectively. A partial structural unit, "R ⁵ O _1/2 " is a group that bonds with the oxygen atom in the D unit, DH unit, T unit, TH unit, or Q unit, and is a group that bonds with the oxygen atom in the organopolysiloxane. It means a bonded hydroxyl group (Si-OH) or a silicon atom-bonded alkoxy group that remains unreacted during the production of organopolysiloxane. MH units mainly exist at the molecular chain ends of organohydrogenpolysiloxane, and DH units exist in the molecular chain of organohydrogenpolysiloxane.

The content of component (B) is such that the silicon-bonded hydrogen atoms in component (B) are 0.5 mole or more per mole of all aliphatic unsaturated carbon-carbon bonds in the composition, The amount of silicon-bonded hydrogen atoms in component (B) is preferably 0.5 to 100 mol, and 0.5 to 60 mol, per 1 mol of all aliphatic unsaturated carbon-carbon bonds in the composition. More preferred is an amount between 0.5 and 40 moles, even more preferred.

Component (C) Component (C) is a catalyst for hydrosilylation reaction. Component (C) may be a single hydrosilylation reaction catalyst, or may be a mixture of two or more hydrosilylation reaction catalysts.

Examples of the hydrosilylation catalyst include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts, with platinum-based catalysts being preferred. Examples of the platinum-based catalyst include platinum-based compounds such as fine platinum powder, platinum black, fine platinum-supported silica powder, activated carbon supporting platinum, chloroplatinic acid, alcoholic solutions of chloroplatinic acid, platinum olefin complexes, and platinum alkenylsiloxane complexes. are exemplified, with platinum alkenylsiloxane complexes being particularly preferred. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples include alkenylsiloxanes in which some of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups, etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the stability of this platinum-alkenylsiloxane complex is good. In addition, since the stability of this platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1 ,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1 , 3,5,7-Tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and other alkenylsiloxanes and dimethylsiloxane oligomers and other organosiloxane oligomers are preferably added, and in particular, alkenylsiloxanes are added. It is preferable.

Component (C) is preferably one that exhibits activity even at relatively low temperatures. Specifically, those that exhibit activity in the composition in the temperature range of 0 to 200°C and promote the hydrosilylation reaction are preferred. In addition, component (C) is preferably a hydrosilylation reaction catalyst in which the curing reaction does not substantially proceed at temperatures below 80°C in the presence of component (D); However, it is particularly preferable that the hydrosilylation reaction catalyst is capable of promoting the hydrosilylation reaction and curing the entire composition by heating at a high temperature of 150° C. or higher.

The content of component (C) varies depending on the type of catalyst and the type of composition, but is usually an amount such that the metal atoms in the catalyst are in the range of 0.1 to 200 ppm by mass based on the composition. and may be in the range of 0.1 to 150 ppm, or 0.1 to 100 ppm.

(D) Component One of the characteristics of the composition of the present invention is that it contains (D) a phosphorus-containing hydrosilylation reaction retarder. A phosphorus-containing hydrosilylation reaction retarder is a component that can strongly suppress the hydrosilylation reaction at low temperatures and adjust the curing reaction. By selectively using such a retarder, the Regardless of the form, it is possible to design a cured reactive silicone pressure-sensitive adhesive composition that has excellent storage stability, handling workability, and moldability. Further, component (D) may be a single phosphorus-containing hydrosilylation reaction retarder, or may be a mixture of two or more.

The phosphorus-containing hydrosilylation reaction retarder is at least one type selected from the group consisting of phosphine compounds, phosphoric acid compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorous compounds, and phosphonous compounds. is preferred.

The phosphine compounds include diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, tripropylphosphine, dicyclohexylphenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1 ,2-bis(diphenylphosphino)propane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 2,3-bis(diphenylphosphino)butane, 1,5 -Bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, bis(2-diphenylphosphinoethyl)phenylphosphinebis(diphenylphosphino)acetylene, 1,1-bis(diphenylphosphino) Ethylene, 1,2-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphino)ferrocene, 1,3-bis(dicyclohexylphosphino)propane, 1,2-bis(dimethylphosphino)ethane, Preferably, it is at least one compound selected from the group consisting of 1,2-bis(dimethylphosphino)benzene and 1,2-bis(diphenylphosphino)benzene.

The phosphoric acid compound is preferably at least one compound selected from the group consisting of triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, and diphenylmethyl phosphate. .

The phosphonic acid compound is preferably at least one compound selected from the group consisting of methylphosphonic acid, dimethyl, diethyl methylphosphonate, dipropyl methylphosphonate, dibutyl methylphosphonate, diethyl phenylphosphonate, and dipropyl phenylphosphonate. .

The phosphine oxide compound may be at least one compound selected from the group consisting of diphenylphosphine oxide, triphenylphosphine oxide, dimethylphenylphosphine oxide, diethylphenylphosphine oxide, tripropylphosphine oxide, and tributylphosphine oxide. preferable.

The phosphorous compounds include triphenyl phosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, diphenyl phosphite, dimethyl phosphite, diethyl phosphite, Preferably, it is at least one compound selected from the group consisting of dipropyl phosphite and dibutyl phosphite.

The phosphonous acid compound is preferably at least one compound selected from the group consisting of dimethyl phenylphosphonite, diethyl phenylphosphonite, and dipropyl phenylphosphonite.

The phosphorus-containing hydrosilylation reaction retarder is preferably a phosphine compound, particularly preferably bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, or 1,3-bis(diphenylphosphino). fino) propane.

(D) The composition of the present invention in which a phosphorus-containing hydrosilylation reaction retarder is selectively used has an improved pot life and can improve handling and workability. Furthermore, even in the form of a single composition, it has excellent storage stability, ease of handling, and moldability, and can be quickly cured by heating at high temperatures to obtain high adhesive strength. It is possible. In addition, the phosphorus-containing hydrosilylation reaction retarder suppresses the progress of the curing reaction due to addition of the hydrosilylation catalyst or heating and melting during molding of the composition, so the present invention provides sufficient curing reactivity and moldability. It is possible to provide a heat-meltable curing reactive silicone pressure-sensitive adhesive composition and a molded product thereof having the following properties. Note that, if another hydrosilylation reaction retarder is used in place of component (D), the technical effect cannot be achieved.

The content of the phosphorus-containing hydrosilylation reaction retarder (D) is not particularly limited, but is, for example, 0.01% per mole of metal atoms, preferably platinum-based metal atoms, in component (C) in the composition. The amount is preferably from 1,000 mol to 1,000 mol, particularly preferably from 0.1 to 500 mol, and particularly preferably from 0.30 to 10 mol. This is because if the content of this retarder is less than the lower limit of the above range, it will be difficult to form this composition into a single composition (one-component, etc.), and the viscosity will thicken in a relatively short time even at room temperature. This is because there is a problem that the hot-melt adhesive sheet no longer exhibits tackiness, and the curing reaction progresses at the stage of heating and melting the hot-melt adhesive sheet. However, this is because the curing reaction becomes difficult to proceed. In addition, when the amount of component (D) used is in the range of 0.30 to 10 mol per 1 mol of metal atoms in component (C), the composition of the present invention is applied in a thin film. Even in such cases, a rapid curing reaction can be achieved by heating at 150° C. or higher.

Component (E) The composition of the present invention contains (E) a siloxane unit (M unit) represented by R ₃ SiO _1/2 (wherein R independently represents a monovalent organic group) in the molecule. And, it can further contain an organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO _4/2 . Component (E) may be a single organopolysiloxane resin or a mixture of two or more organopolysiloxane resins.

Component (E) is a component that imparts pressure-sensitive adhesive properties to the cured reactive silicone pressure-sensitive adhesive composition of the present invention or its cured product, and can impart high adhesion to various substrates or substrates. Component (E) contains a siloxane unit (M unit) represented by (a) R ₃ SiO _1/2 (wherein R independently represents a monovalent organic group) in the molecule, and ( b) An organopolysiloxane resin containing siloxane units (Q units) represented by SiO _4/2 .

The molar ratio of (a) M units to (b) Q units is preferably in the range of M units:Q units = 0.50:1.00 to 1.50:1.00, preferably 0.55:1. The range of 0.00 to 1.20:1.00 is more preferable, and the range of 0.60:1.00 to 1.10:1.00 is even more preferable. The above molar ratio can be easily measured by ²⁹ Si nuclear magnetic resonance.

Component (E) has the general unit formula: (R ₃ SiO _1/2 ) _a (SiO _4/2 ) _b (wherein R is independently a monovalent organic group, and a and b are each positive numbers. The organopolysiloxane resin is preferably an organopolysiloxane resin represented by the following formula: a+b=1, a/b=0.5 to 1.5.

The component (E) may be composed only of (a) M units and (b) Q units, but may include R ₂ SiO _2/2 units (D units) and/or RSiO _3/2 units (T units). May include. In addition, in the formula, R independently represents a monovalent organic group. The total content of (a) M units and (b) Q units in component (E) is preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 100% by weight.

The monovalent organic group is not particularly limited, and can be divided into, for example, an aliphatic unsaturated carbon-carbon bond-containing group and an aliphatic unsaturated carbon-carbon bond-free group.

The aliphatic unsaturated carbon-carbon bond-containing group and the aliphatic unsaturated carbon-carbon bond-free group include a monovalent unsaturated hydrocarbon group and an oxygen atom-containing monovalent unsaturated hydrocarbon group, respectively; Included are monovalent saturated hydrocarbon groups and oxygen atom-containing monovalent saturated hydrocarbon groups.

Examples of monovalent unsaturated or saturated hydrocarbon groups include substituted or unsubstituted monovalent hydrocarbon groups having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms. Examples include valently unsaturated hydrocarbon groups and substituted or unsubstituted monovalent saturated hydrocarbon groups having 1 to 12 carbon atoms.

Examples of the unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms include vinyl group, allyl group, propenyl group, etc. group, butenyl group, pentenyl group, hexenyl group, and other alkenyl groups. Examples of substituted monovalent unsaturated hydrocarbon groups having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms include, for example, these monovalent unsaturated hydrocarbon groups. Examples include groups in which some of the hydrogen atoms are replaced with halogen atoms (fluorine, chlorine, bromine, or iodine), etc.

Examples of unsubstituted monovalent saturated hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, pentyl group, hexyl group, and octyl group; cyclohexyl group, cycloheptyl group, etc. Examples include cycloalkyl groups; aryl groups such as phenyl, tolyl and xylyl groups; aralkyl groups such as benzyl, α-methylstyryl and 2-phenylethyl groups. Examples of substituted monovalent saturated hydrocarbon groups having 1 to 12 carbon atoms include monovalent unsaturated hydrocarbon groups in which some of the hydrogen atoms are substituted with halogen atoms (fluorine, chlorine, bromine or iodine), etc. There are many things that can be mentioned. Specifically, fluorinated monovalent saturated hydrocarbon groups, such as 3,3,3-trifluoropropyl group, 4,4,5,5,5-pentafluorobutyl group, 3,3,4,4, Perfluoroalkyl groups such as 5,5,6,6,6-nonafluorohexyl groups; chlorinated monovalent saturated hydrocarbon groups, such as chloroalkyl groups such as 3-chloropropyl groups, chlorophenyl groups such as dichlorophenyl groups can be mentioned.

The monovalent saturated hydrocarbon group is preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. The substituted or unsubstituted alkyl group having 1 to 12 carbon atoms is preferably a methyl group. The monovalent unsaturated hydrocarbon group is preferably a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms. The substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms is preferably a vinyl group.

Examples of the oxygen atom-containing monovalent unsaturated or saturated hydrocarbon group include substituted or unsubstituted oxygen atom-containing monovalent unsaturated hydrocarbon groups having 2 to 12 carbon atoms, and 1 to 12 carbon atoms. Examples include substituted or unsubstituted oxygen atom-containing monovalent saturated hydrocarbon groups.

Examples of the substituted or unsubstituted oxygen atom-containing monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms include alkenyloxyalkyl groups, acryloxyalkyl groups, methacryloxyalkyl groups, and the like.

Examples of the alkenyloxyalkyl group include an allyloxymethyl group and a 3-allyloxypropyl group. Examples of the acryloxyalkyl group include an acryloxymethyl group and a 3-acryloxypropyl group. Examples of the methacryloxyalkyl group include methacryloxymethyl group and 3-methacryloxypropyl group.

Examples of the substituted or unsubstituted oxygen atom-containing monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include an alkoxy group having 1 to 12 carbon atoms.

Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, and isopropoxy group.

A part of these groups may be substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or the like.

The organopolysiloxane resin as component (E) may contain a small amount of hydroxyl groups bonded to silicon atoms. The content of hydroxyl groups is preferably 0.2 mol or less, more preferably 0.1 mol or less, per 1 mol of all silicon atoms.

In addition, when the organopolysiloxane resin of component (E) contains an alkoxy group bonded to a silicon atom such as a methoxy group or an ethoxy group, the content thereof is 0.2 mol or less per 1 mol of total silicon atoms. is preferable, and 0.1 mol or less is more preferable.

((E1) Curing reactive organopolysiloxane resin)
In one aspect of the present invention, at least a portion of component (E) contains (Alk)R' ₂ SiO _1/2 in the (E1) molecule (wherein Alk independently represents an aliphatic unsaturated carbon-carbon A siloxane unit (M unit) represented by a bond-containing group, R' each independently represents an aliphatic unsaturated carbon-carbon bond-free group, and a siloxane unit represented by SiO _4/2 It may be a curing reactive organopolysiloxane resin containing at least (Q unit).

In the above embodiment, the aliphatic unsaturated carbon-carbon bond-containing group that is Alk is preferably an alkenyl group, an alkenyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, as described above. Further, the aliphatic unsaturated carbon-carbon bond-free group that is R' is preferably an alkyl group, an aryl group, or an aralkyl group as described above. Further, some of these groups may be substituted with halogen atoms or the like. From an industrial point of view, the aliphatically unsaturated carbon-carbon bond-containing group Alk may be a vinyl, allyl or hexenyl group, and the aliphatically unsaturated carbon-carbon bond-free group R' is Preferably, it is a methyl group, a phenyl group, or the like.

In the above embodiment, when a component (E) other than the curing-reactive organopolysiloxane resin (E1) is present, the component (E) is preferably non-curing-reactive. In this case, R of the non-curing reactive component (E) is preferably the aforementioned aliphatic unsaturated carbon-carbon bond-free group, more preferably an alkyl group, aryl group or aralkyl group. Further, some of these groups may be substituted with halogen atoms or the like. From an industrial standpoint, the aliphatic unsaturated carbon-carbon bond-free group represented by R is preferably a methyl group, a phenyl group, or the like.

The proportion of curing reactive organopolysiloxane resin (E1) in component (E) is not particularly limited, but in order to achieve appropriate hardness for the composition of the present invention or its cured product as an adhesive material. is preferably 50% by weight or less of component (E), more preferably 30% by weight or less, and even more preferably 20% by weight or less, when the entire component (E) is 100% by weight. Suitably, the content of component (E1) in component (E) is in the range of 0 to 20% by mass, particularly preferably in the range of 0 to 15% by mass, and the content of component (E1) in component (E) is preferably in the range of 0 to 15% by mass. The adhesive material made of the above material can have appropriate hardness and flexibility as an adhesive layer for display devices, solar cell modules, etc.

As such component (E), for example,
(Me ₃ SiO _1/2 ) _0.45 (SiO _4/2 ) _0.55 (HO _1/2 ) _0.05
(Me ₃ SiO _1/2 ) _0.40 (SiO _4/2 ) _0.60 (HO _1/2 ) _0.10
(Me ₃ SiO _1/2 ) _0.52 (SiO _4/2 ) _0.48 (HO _1/2 ) _0.01
(Me ₃ SiO _1/2 ) _0.40 (Me ₂ ViSiO _1/2 ) _0.05 (SiO _4/2 ) _0.55 (HO _1/2 ) _0.05
(Me ₃ SiO _1/2 ) _0.45 (SiO _4/2 ) _0.55 (MeO _1/2 ) _0.10
(Me ₃ SiO _1/2 ) _0.25 (Me ₂ PhSiO _1/2 ) _0.20 (SiO _4/2 ) _0.55 (HO _1/2 ) _0.05
(Me ₃ SiO _1/2 ) _0.40 (Me ₂ SiO _2/2 ) _0.05 (SiO _4/2 ) _0.55 (HO _1/2 ) _0.05
(Me ₃ SiO _1/2 ) _0.40 (MeSiO _3/2 ) _0.05 (SiO _4/2 ) _0.55 (HO _1/2 ) _0.05
(Me ₃ SiO _1/2 ) _0.40 (Me ₂ SiO _2/2 ) _0.05 (MeSiO _3/2 ) _0.05 (SiO _4/2 ) _0.50 (HO _1/2 ) _0.05
(Me: methyl group, Ph: phenyl group, Vi: vinyl group, MeO: methoxy group, HO: silicon atom-bonded hydroxyl group. In addition, in order to express the relative amount of hydroxyl group to silicon atom, the sum of the subscripts of silicon atom-containing units The amount is set to 1, and the subscript of (HO) _1/2 unit indicates the relative amount)
can be mentioned.

Component (E) is a component that imparts pressure-sensitive adhesive properties and heat-melting properties to the cured reactive silicone pressure-sensitive adhesive composition of the present invention or its cured product, and therefore the amount thereof to be blended can be selected as desired. can do. For example, component (E) may range from 0.1% by mass to 90% by mass based on the total mass of component (A), component (B), and component (E). If the amount of component (E) exceeds the above upper limit, the curing reactive silicone pressure-sensitive adhesive composition of the present invention or its cured product becomes too hard and may not be particularly suitable for use as a pressure-sensitive adhesive.

When the cured reactive silicone adhesive composition of the present invention is in liquid form and the cured product thereof is designed to have slightly to medium adhesive strength, component (E) is component (A), It is preferably in the range of 0.1% by mass to 40% by mass, and preferably in the range of 0.1% by mass to 30% by mass, based on the total mass of component (B) and component (E). good. However, in the case of a slightly adhesive curing reactive silicone adhesive composition, the amount of component (E) to be blended should be adjusted relative to the total mass of component (A), component (B), and component (E) above. However, the content may be designed to be 0.1% by mass or less, and is preferable. This is because the cured product can be used as a slightly sticky adhesive layer even if it does not contain component (E) at all.

When the cured reactive silicone pressure-sensitive adhesive composition of the present invention or its cured product is designed to have a certain degree of strong adhesive strength and pressure-sensitive adhesive properties, the blending amounts of component (E) should be as follows: component (A), component (B). It is preferably in the range of 35% by mass to 90% by mass based on the total mass of components () and (E). On the other hand, when the blending amount of component (E) exceeds 90% by mass, the glass transition point (Tg) of the entire composition increases, the entire composition becomes excessively hard, and handling workability as an adhesive is reduced. This can be difficult and is not desirable.

The cured reactive silicone adhesive composition of the present invention has sufficient adhesive strength and heat meltability, and the composition as a whole is non-flowable at 25°C and has a softening point between 25°C and 150°C. In the case of designing the product to have the following properties, the blending amount of component (E) is 55% to 90% by mass based on the total mass of component (A), component (B), and component (E). A range of 60 to 85% by weight is particularly preferred. In addition, when preparing a non-flowable composition at 25° C., it is preferable not to use the solvent described below. If the amount of component (E) is within the above range, the curing reactive silicone adhesive composition of the present invention will have sufficient adhesive strength for temporary fixation before the curing reaction. In addition, it is possible to design a cured product that has adhesive strength to the extent that permanent adhesion between members is possible through a curing reaction.

(F) Component As mentioned above, the composition of the present invention can be designed as a solvent-free composition or a heat-melt composition, but it may further contain (F) a solvent. . (F) By using a solvent, it is possible to reduce the viscosity and thixotropy of the entire composition, improving handling and coating properties, and by using a small amount of an organic solvent, the wettability of the composition to the substrate can be improved. Improvements may be made, and the cured reactive silicone adhesive compositions of the present invention can be formulated to be applicable to a variety of processes. In particular, in order to form the composition of the present invention into a thin film or to apply it in a desired pattern by printing, it is possible and preferable to use the composition of the present invention with a solvent added thereto.

The type of solvent as component (F) is not particularly limited, as long as it dissolves the composition of the present invention and provides a uniform solution. For example, a low molecular weight siloxane solvent or an organic solvent may be used. In particular, it is preferable to use organic solvents, such as aliphatic hydrocarbons such as normal hexane, normal pentane, normal heptane, normal octane, isooctane, and decalin; aromatic hydrocarbons such as toluene, xylene, and mesitylene; diisopropyl ether; Examples include ethers such as dibutyl ether and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and glycol esters such as propylene glycol monomethyl acetate and dipropylene glycol monomethyl ether acetate.

The amount of the solvent as component (F) is not particularly limited, but when the sum of components (A) to (E) above is 100 parts by mass, it is used in the range of 0 to 9900 parts by mass. The amount of solvent to be used can be appropriately designed depending on the coating conditions such as the substrate and the thickness of the coating film. In addition, when using a solvent as a so-called dispersion medium to reduce the overall viscosity of the composition and improve coating properties, the sum of the above components (A) to (E) is, for example, 50 parts by mass per 100 parts by mass. Part or more of the solvent may be used, but when the solvent is used for the purpose of improving wettability, it is also possible to use a relatively small amount of solvent, for example, 20 parts by mass or less, and ,preferable.

Unsaturated Aliphatic Hydrocarbons The compositions of the present invention may optionally further include unsaturated aliphatic hydrocarbons. Unsaturated aliphatic hydrocarbons contain aliphatic unsaturated bonds that participate in hydrosilylation reactions, etc., so they can be used as reactive diluents that function as crosslinking components during curing reactions and as the solvents mentioned above. Can be done. More specifically, unsaturated aliphatic hydrocarbons are hydrocarbon compounds having 8 to 18 carbon atoms and having at least one aliphatic unsaturation within the molecule. The unsaturated aliphatic hydrocarbon may be linear or branched, and the aliphatic unsaturated moiety may be in the middle or at the end, and there may be two or more aliphatic unsaturated moieties in the molecule. It is particularly preferred to have a carbon-carbon double bond which is a saturated portion. Such unsaturated aliphatic hydrocarbons include alkenes having 8 to 18 carbon atoms, preferably alkenes having 12 to 14 carbon atoms, having a carbon-carbon double bond at the end of the molecular chain, and are particularly suitable for reaction. When used as a diluent, dodecene, tetradecene, hexadecene, and octadecene are exemplified, and tetradecene is preferably exemplified.

The amount of unsaturated aliphatic hydrocarbon to be used is not particularly limited, but when the sum of components (A) to (E) above is 100 parts by mass, it is preferably 0.1 to 10 parts by mass. ranges from 0.1 to 7.5 parts by mass.

Other components The composition of the present invention may optionally contain other organopolysiloxanes, adhesive agents, inorganic fillers such as silica, glass, alumina, and zinc oxide; organic resin fine powder such as polymethacrylate resin; It can contain a phosphor, a heat resistant agent, a dye, a pigment, a flame retardant agent, a solvent, and the like. The amounts and methods of adding these optional ingredients are known to those skilled in the art.

[Production method]
The composition of the present invention can be produced by mixing components (A) to (D), if necessary, component (E), component (F), and/or other optional components. Although the composition of the present invention may be prepared by mixing at the time of use, it is preferable to prepare the composition by mixing in advance before use.

By using the component (D), the composition of the present invention allows the curing reaction to occur even when the hydrosilylation reaction catalyst (C) coexists with the components (A), (B), etc. when heated and melted at room temperature. As a result, even in the form of a single composition, the curing reaction may progress during the mixing operation, resulting in thickening or gelation, or the curing reactivity of the mixture or molded product may decrease within a few hours to several days. Loss is effectively prevented. Therefore, it is possible to stably produce the present composition or a molded product thereof using a simple process.

The composition of the present invention may be liquid or non-flowing at 25°C, and the method for preparing it is not particularly limited, but may be prepared by the following method.

When the composition of the present invention is a liquid composition having fluidity at 25° C., the mixing is carried out by homogeneously mixing the respective components using mechanical force. If necessary, a solvent as component (F) may be added, and the mixture may be prepared by mixing at a temperature of 0 to less than 150° C. using a known stirrer or kneader.

In the case where the composition of the present invention is non-flowable at 25°C and has heat-melting properties, for example, components (A), (B), and (E) are mixed in a temperature range of 80°C to 120°C. It can be prepared by adding and mixing a mixture of components (C) and (D) in advance while heating and kneading. In the above temperature range, the entire composition is softened and the mixture of components (C) and (D) can be uniformly dispersed throughout the composition. There is a practical benefit of avoiding cohesive failure. On the other hand, if the temperature is less than the lower limit, softening may be insufficient and it may be difficult to uniformly disperse the mixture of components (C) and (D) throughout even if mechanical force is used. On the other hand, if the temperature exceeds the above upper limit, component (C) may react during mixing, resulting in significant thickening or hardening of the entire mixture and loss of heat-melting properties, which is not preferable. The mixer used in this manufacturing method is not limited, and may include a kneader with heating/cooling functions, a Banbury mixer, a Henschel mixer, a planetary mixer, a 2-roll mill, a 3-roll mill, a Ross mixer, a laboplast mill, etc. , a single-screw extruder, a twin-screw extruder, or other continuous heating kneading device equipped with a heating/cooling function may be used, and is not particularly limited. Ru. In terms of processing time, a continuous type mixer such as a single-screw extruder or a twin-screw extruder may be used, or a batch-type mixer such as a laboplast mill may be used.

[Use of composition]
When the curable reactive silicone pressure-sensitive adhesive composition of the present invention has fluidity at 25° C., it can be coated onto a substrate to form a coating film, and heated to form a cured product. Examples of the coating method include offset coating, offset gravure, roll coating, reverse roll coating, air knife coating, curtain coating, and comma coating. Although the temperature during coating is not particularly limited, it is preferable to coat at a temperature of less than 150°C. In addition, when the composition of the present invention is applied in the form of a thin film, for the purpose of adjusting the overall viscosity of the composition, improving wettability, etc., it may be applied onto a substrate in a form containing (F) a solvent, for example. It is also possible, and preferred, to form a coating film by heating.

When the cured reactive silicone pressure-sensitive adhesive composition of the present invention is non-flowable at 25° C. and has heat-melting properties, it can be molded into a desired shape and used. For example, such a molded product can be designed to have sufficient adhesive strength for temporary fixation depending on the content of component (E), and can be placed on a specific adherend. By doing so, it can be used as a heat-melting adhesive material.

The composition of the present invention can be processed into objects of various shapes by heating and melting the composition preferably at a temperature of 80° C. or more and less than 150° C., and then cooling it. For example, the composition has a thickness of 5 μm to 5 mm. It can be in the form of a sheet, powder, or tablet. Specifically, the composition of the present invention can be heated and melted using an apparatus having heating and extrusion functions, and processed into an object of a desired shape. Note that unless the object is heated to 150°C or higher to initiate the curing reaction, it maintains its curing reactivity and heat-melting properties, so it can be used as a heat-melting adhesive in the form of members, parts, sheets, etc. It is particularly preferable to use

As mentioned above, the composition of the present invention can be designed to have sufficient adhesive strength for temporary fixation depending on the content of component (E), for example, and can be used as a heat-melting adhesive. However, a sticky cured product (including a semi-cured product) can be formed by heating the composition to 150° C. or higher to perform a curing reaction. Therefore, the composition of the present invention is useful as various potting agents, sealants, adhesives/adhesives, and preferably as optical adhesives/adhesives, particularly as optical adhesives/adhesives for displays. Useful as an adhesive. In particular, the composition of the present invention has sufficient adhesive strength for temporary fixing before the curing reaction and is heat-meltable, so it can be used as a gap filler that easily follows the irregularities and gaps of the adherend. It is possible to form an adhesive layer with excellent properties. Furthermore, the cured product is less colored and less likely to become cloudy at high temperatures or under high temperature/high humidity, so it can be used as a fixing layer or adhesive layer between components that make up laminates such as displays and solar cell modules. Extremely useful.

(cured product)
The composition of the present invention can be a cured product. The cured product is obtained by (further) carrying out a hydrosilylation reaction on the composition of the present invention to (completely or finally) cure the composition of the present invention. For example, the composition can be cured by heating the composition at a temperature of 150° C. or higher to carry out a hydrosilylation reaction. The heating time depends on the type and amount of each component in the composition, but is usually 0.2 to 4 hours, preferably 0.5 to 2 hours.

The cured product of the present invention can be used as various materials. Here, a cured product means that it does not flow even when heated to 200° C. or higher. The hardness of this cured product is not particularly limited, but usually ranges from gel-like with a penetration of 70 or less to resin-like with a Shore D hardness of 80.

Preferably, the cured product of the present invention is light-transmissive, more preferably transparent. A light-transmitting, particularly transparent cured product can be suitably used for optical purposes.

The cured product of the present invention can have pressure-sensitive adhesive properties. The adhesive strength of the cured product is not particularly limited, but can be measured as follows by a method according to JIS Z0237.

<For liquid composition at 25°C>
An adhesive layer with a thickness of 50 μm obtained by curing the composition was attached to a SUS steel plate, and the adhesive strength was measured at a tensile rate of 300 mm/min using a 180° peel test method (measured at a width of 20 mm). (converted to display unit gf/inch) is preferably 0.1 gf/inch or more, particularly preferably 0.1 gf/inch to 10 kgf/inch, and preferably 0.2 gf/inch to 10 kgf/inch. is even more preferable. However, it goes without saying that these adhesive strengths can be designed within a desired range from slight adhesiveness to strong adhesiveness to permanent adhesiveness.

<In the case of a heat-meltable composition that is non-flowable at 25°C>
An adhesive layer with a thickness of 200 μm obtained by curing the composition was attached to a SUS steel plate, and the adhesive strength was measured at a tensile rate of 300 mm/min using a 180° peel test method (measured at a width of 20 mm). (converted to display unit gf/inch) is preferably 0.1 gf/inch or more, particularly preferably 0.1 gf/inch to 10 kgf/inch, and preferably 0.2 gf/inch to 10 kgf/inch. is even more preferable. However, it goes without saying that these adhesive strengths can be designed within a desired range from slight adhesiveness to strong adhesiveness to permanent adhesiveness.

The cured product of the present invention can have a certain degree of stretchability or flexibility. Therefore, the cured product of the present invention can be used as an elastic adhesive member.

(Adhesive)
The cured reactive silicone pressure-sensitive adhesive composition of the present invention and its cured product can be used as a pressure-sensitive adhesive.

The adhesive material of the present invention can have high adhesive strength and can adhere or adhere well to various adherends. Further, the adhesive material of the present invention can form an adhesive layer that is unlikely to cause cohesive failure when peeled from an adherend, but depending on the application, this is not limited to this and may be accompanied by cohesive failure.

Therefore, the behavior of the cured reactive silicone pressure-sensitive adhesive composition of the present invention and its cured product pressure-sensitive adhesive layer when peeled from an adherend can be preferably controlled depending on the intended use. For example, in applications where the adhesive is expected to act as a (pressure-sensitive) adhesive, there may be no or only a small amount of residue on the surface of the adherend. On the other hand, depending on the application, it may not be a problem to exhibit high adhesion that may cause cohesive failure.

Use as a heat-melting adhesive For example, depending on the amount of component (E) mentioned above, the cured reactive silicone adhesive composition of the present invention has a non-flowable and hot-melt property at 25°C as a whole. It can be designed as a composition. In this case, the cure-reactive silicone pressure-sensitive adhesive composition of the present invention can be used as a heat-meltable pressure-sensitive adhesive having excellent moldability, gap-filling properties, and adhesive strength before the curing reaction. Furthermore, although the cured product of the curing-reactive silicone pressure-sensitive adhesive composition of the present invention substantially loses heat-melting properties and curing reactivity, it can be used as a pressure-sensitive adhesive material with excellent adhesive strength. For this reason, adhesives made of curing reactive silicone adhesive compositions can be used to temporarily fix components or to form adhesive layers on adherends that take advantage of their gap-filling properties against irregularities and gaps. After temporarily fixing, arranging, and bonding, the adhesive made of the cured reactive silicone adhesive composition is heated to 150°C or higher to spread the adhesive made of the cured product between the adherends. It may be formed. In addition, since the adhesive material made of the cured product of the curing reactive silicone adhesive composition of the present invention can itself be used as a pressure-sensitive adhesive, heating of the curing reactive silicone adhesive composition of the present invention It may be molded into a sheet or the like by utilizing its melting properties, then cured, and then handled alone as an adhesive member having a desired shape.

Use as adhesive material consisting of cured product The cured reactive silicone adhesive composition of the present invention can be heated at 150°C or higher to form an adhesive cured product (cured reaction product). The cured product can be used as an adhesive layer, an adhesive layer, especially a pressure-sensitive adhesive layer (PSA layer), and as an adhesive material for bonding members together by pressure bonding. As described below, since the cured product can be used alone as an adhesive material, the cured product of the cured reactive silicone adhesive composition of the present invention can be handled alone as an adhesive film or a pressure-sensitive adhesive film. After or at the same time as placing the cured reactive silicone adhesive composition on a member in the form of a liquid or heat-melting adhesive as described above, the cured reactive silicone adhesive composition is heated to 150° C. or higher to be cured to form an adhesive. You may. In addition, whether the state before curing is a liquid composition that has fluidity at 25°C or a hot-melt composition that is non-flowable at 25°C, the cured product cannot be cured with an adhesive (especially an adhesive). layer).

[Laminated body]
A laminate including a layer made of the cured reactive silicone pressure-sensitive adhesive composition of the present invention or a layer or member made of a cured product of the composition can be provided. The laminate includes, but is not particularly limited to, an adhesive sheet (including an adhesive sheet and a pressure-sensitive adhesive (PSA) sheet), a releasable material in which they are laminated on a sheet-like member provided with a release layer. It may be a laminate.

Adhesive Sheet Next, an adhesive sheet, which is a type of laminate according to the present invention, will be explained.

The adhesive sheet of the present invention is
at least one sheet-like substrate;
comprising at least one adhesive layer formed on the sheet-like base material,
The adhesive layer contains the above-mentioned curing reactive silicone adhesive composition or a cured product thereof.

Uncured Adhesive Sheet The cured reactive silicone adhesive composition contained in the adhesive layer of the adhesive sheet of the present invention may be in an uncured state. Such an adhesive sheet can be easily obtained by using a non-flowable hot-melt composition at 25°C.

The adhesive sheet of the present invention can be prepared, for example, by applying the cured reactive silicone adhesive composition of the present invention in a heated molten state onto a sheet-like base material to form an adhesive layer of a predetermined thickness, and as needed. It can be manufactured by semi-curing the adhesive layer.

The type of sheet-like base material is not particularly limited, and polyester films, polyolefin films, polycarbonate films, acrylic films, etc. can be used as appropriate. Preferably, the sheet-like substrate is non-porous.

Coating methods for sheet-like substrates include offset coating, offset gravure, roll coating using an offset transfer roll coater, reverse roll coating, air knife coating, curtain coating using a curtain flow coater, comma coating, Meyer bar, etc. , and other known methods used for the purpose of forming layers can be used without limitation.

In the adhesive sheet of the present invention, the sheet-like base material preferably includes at least one release layer, and the release layer is preferably in contact with the adhesive layer. Thereby, the adhesive layer can be easily peeled off from the sheet-like base material. The release layer is sometimes called a release liner, a separator, a release layer, or a release coating layer, and is preferably a release agent such as a silicone release agent, a fluorine release agent, an alkyd release agent, or a fluorosilicone release agent. A release layer having coating ability, a substrate that physically forms fine irregularities on the surface of the substrate, and a substrate itself that is difficult to adhere to the adhesive layer made of the cured reactive silicone pressure-sensitive adhesive composition of the present invention or its cured product. It may be. Particularly in the laminate of the present invention, it is preferable to use a release layer formed by curing a fluorosilicone release agent.

The adhesive sheet of the present invention can be used by, for example, applying the adhesive layer to an adherend and then peeling the uncured adhesive sheet from the sheet-like base material. Note that, as described later, the adhesive sheet may be heated to 150° C. or higher to form a cured product and then peeled off for use.

When the adhesive sheet of the present invention is a hot-melt adhesive sheet that is a molded product of a hot-melt composition that is non-flowable at 25°C, after applying the adhesive sheet to an adherend, the final By heating the adhesive sheet before curing, the adhesive sheet becomes flexible or fluid, and for example, even if the adherend surface is uneven, the adhesive layer can be filled without any gaps. . As a heating means for the adhesive sheet, for example, various constant temperature baths, hot plates, electromagnetic heating devices, heating rolls, etc. can be used. In order to perform lamination and heating more efficiently, for example, an electric heat press machine, a diaphragm type laminator, a roll laminator, etc. are preferably used.

In this case, if the softening temperature of the hot-melt adhesive sheet is 50° C. or higher, sufficient processing characteristics and storage characteristics at room temperature can be achieved. On the other hand, if the softening temperature of the adhesive layer is 100° C. or less, not only can thermal damage to an image display panel etc. be suppressed, but also the adhesive layer can be prevented from flowing too much and protruding. Therefore, the softening temperature of the hot-melt adhesive sheet is preferably 50 to 100°C, especially 55°C or higher or 95°C or lower, and even more preferably 60°C or higher or 90°C or lower.

Adhesive sheet containing cured product The cured reactive silicone adhesive composition contained in the adhesive layer of the adhesive sheet of the present invention may be a cured product. Such an adhesive sheet can be obtained by applying a fluid composition at 25°C to form an adhesive layer of a predetermined thickness, and then heating and curing it at a temperature of 150°C or higher. Moreover, such an adhesive sheet can be obtained by heating and curing the above-mentioned hot-melt adhesive sheet at a temperature of 150°C. Note that the method of coating the sheet-like base material and the use of the sheet-like base material provided with a release layer are the same as described above.

The adhesive sheet of the present invention can be produced by, for example, applying the adhesive layer to an adherend and then curing the cured reactive silicone adhesive composition contained in the adhesive layer by heating etc. It can be used by peeling off the adhesive layer.

As for the adhesive layer, while it is possible to meet the demand for thinning by reducing the thickness, if the thickness is too thin, for example, if there are irregularities on the adhered surface, the adhesive layer may not be able to sufficiently follow the irregularities. There is a possibility that sufficient adhesion force cannot be exerted. From this point of view, the thickness of the adhesive layer is preferably 5 to 10,000 μm, particularly preferably 10 μm or more and 8,000 μm or less, particularly preferably 20 μm or more and 5,000 μm or less.

Pressure-Sensitive Adhesive Sheet Next, a pressure-sensitive adhesive sheet, which is a type of the above-mentioned adhesive sheet, will be explained.

The pressure sensitive adhesive sheet of the present invention is
at least one sheet-like substrate;
comprising at least one pressure-sensitive adhesive layer formed on the sheet-like base material,
The pressure-sensitive adhesive layer contains the above-mentioned curing reactive silicone adhesive composition or a cured product thereof.

Curing can be carried out by performing a hydrosilylation reaction on the composition of the present invention, for example, by heating at 150° C. or higher.

The pressure-sensitive adhesive sheet of the present invention can be produced by, for example, applying the curable reactive silicone adhesive composition of the present invention onto a sheet-like base material to form a layer with a predetermined thickness, and curing the layer to form a pressure-sensitive adhesive sheet. It can be manufactured by forming an adhesive layer.

The type of sheet-like base material is not particularly limited, and polyester films, polyolefin films, polycarbonate films, acrylic films, etc. can be used as appropriate. Preferably, the sheet-like substrate is non-porous.

Coating methods for sheet-like substrates include offset coating, offset gravure, roll coating using an offset transfer roll coater, reverse roll coating, air knife coating, curtain coating using a curtain flow coater, comma coating, Meyer bar, etc. , and other known methods used for the purpose of forming layers can be used without limitation.

In the pressure-sensitive adhesive sheet of the present invention, the sheet-like base material preferably includes at least one release layer, and the release layer is preferably in contact with the pressure-sensitive adhesive layer. Thereby, the pressure-sensitive adhesive layer can be easily peeled off from the sheet-like base material. The release agent contained in the release layer is not particularly limited, and the above-mentioned release agents can be mentioned.

In one embodiment of the pressure-sensitive adhesive sheet of the present invention, there may be two sheet-like base materials.

For example, the pressure sensitive adhesive sheet of the present invention is
a first sheet-like base material;
a second sheet base material,
comprising at least one pressure sensitive adhesive layer formed between a first sheet substrate and a second sheet substrate;
The pressure sensitive adhesive layer may be in contact with the first sheet base material and the second sheet base material.

The pressure-sensitive adhesive sheet of the above form can be produced, for example, by sandwiching the curable reactive silicone adhesive composition of the present invention between a first sheet-like base material and a second sheet-like base material, and pressing or rolling it while heating. It can be manufactured by curing the composition after molding it to a certain thickness.

The first sheet base material may include a first release layer, or the first sheet base material itself may have releasability. Similarly, the second sheet base material may be provided with a second release layer, or the second sheet base material itself may be provided with releasability. When the first sheet substrate and/or the second sheet substrate comprises a first release layer and/or a second release layer, the pressure sensitive adhesive layer is provided with the first release layer and/or the second release layer. Preferably, it contacts the release layer.

Examples of the sheet base material having releasability include a sheet base material made of a material having releasability such as a fluororesin film, or a sheet base material made of a material with releasability such as a polyolefin film, or a material with no or low releasability such as a polyolefin film made of silicone, fluororesin, etc. Examples include sheet substrates made of materials to which a release agent has been added. On the other hand, examples of the sheet base material provided with a release layer include a polyolefin film coated with a release agent such as silicone or fluororesin.

The pressure-sensitive adhesive sheet of the present invention can be used, for example, by applying the pressure-sensitive adhesive layer to an adherend and then peeling the pressure-sensitive adhesive layer from the sheet-like base material.

The thickness of the pressure-sensitive adhesive layer is preferably 5 to 10,000 μm, particularly preferably 10 μm or more and 8,000 μm or less, particularly preferably 20 μm or more and 5,000 μm.

Use as adhesive tape Specific examples of the laminate of the present invention will be further explained below.

For example, the laminate of the present invention may be an adhesive tape, and may include a sheet-like member made of a textile product such as the above-mentioned synthetic resin film/sheet, metal foil, woven fabric, non-woven fabric, or paper, and the above-mentioned adhesive layer. It is characterized by The types of such adhesive tapes are not particularly limited, and include insulating tape, heat-resistant tape, solder masking tape, mica tape binder, temporary fixing tape (particularly including temporary fixing tape for silicone rubber parts, etc.), and splicing tape. (including in particular splicing tape for silicone release paper).

Insulating tapes include, for example, tapes (substrates) made of synthetic resins with insulating properties such as polyvinyl chloride, which are provided with an adhesive material made of the curing reactive silicone adhesive composition of the present invention or a cured product thereof as an adhesive layer. can be mentioned. Such an insulating tape can be suitably used, for example, in applications requiring electrical insulation, such as repairing the insulation coating of electric wires.

Examples of the heat-resistant tape include tapes (substrate) made of a heat-resistant synthetic resin such as polyimide, and an adhesive layer comprising the cured reactive silicone adhesive composition of the present invention or a cured product thereof. be able to. Such a heat-resistant tape can be suitably used in applications where heat resistance is required, such as repairing mufflers of automobiles and the like. Since the adhesive layer of the adhesive tape of the present invention is silicone-based, it has excellent heat resistance.

Solder masking tape is a type of insulating tape or heat-resistant tape, and can be used for masking during the soldering process of printed circuit boards.

Mica tape is a type of insulating tape or heat-resistant tape, and can be obtained by impregnating a mica sheet (substrate) with an appropriate amount of binder and heating and compressing it as necessary. It may also be processed into a tape by laminating it with a reinforcing material such as a sheet. The cured reactive silicone pressure-sensitive adhesive composition of the present invention or its cured product can be used as the binder. Furthermore, the mica tape may be provided with an adhesive layer, and the cured reactive silicone adhesive composition of the present invention or a cured product thereof may be used as the adhesive layer.

The temporary fixing tape is a tape used for various temporary fixing purposes, and includes an adhesive layer made of the curing reactive silicone adhesive composition of the present invention or a cured product thereof. Since the adhesive layer has excellent adhesiveness and releasability, the temporary fixing tape of the present invention is suitable for temporary fixing. Since the adhesive layer is silicone-based, it has excellent affinity for silicone rubber parts, and can be particularly suitably used for temporarily fixing silicone rubber parts.

Splicing tape is a tape used to connect films, etc., and includes an adhesive layer made of the cured reactive silicone adhesive composition of the present invention or a cured product thereof. Since the adhesive layer has excellent adhesive properties, the splicing tape of the present invention is suitable for connecting films and the like. Since the adhesive layer is silicone-based, it has adhesive properties even on a silicone release-treated surface, and can be particularly suitably used for connecting silicone release paper.

Article The adhesive material made of the cured reactive silicone adhesive composition of the present invention or its cured product can be used for bonding various objects.

Thus, the present invention
at least one substrate;
An article comprising at least one adhesive component, the article comprising:
The present invention also relates to an article in which the adhesive component includes an adhesive comprising the cured reactive silicone adhesive composition of the present invention or a cured product thereof.

The shape of the base body and the adhesive material component is arbitrary, and can be made into various three-dimensional shapes. The properties of the adhesive material are as described above.

The adhesive component can be present on or in the substrate. Preferably, at least a portion of the substrate adheres to the adhesive component.

The adhesive component has adhesive strength and can be well bonded to various other substrates. Furthermore, the adhesive component may be permanently bonded to another substrate, and the adhesive component may be designed to have an adhesive mode in which cohesive failure does not occur and interfacial peeling occurs when the adhesive component is peeled from the other substrate. is also possible.

Similarly, the present invention
at least one substrate,
An article comprising a laminate comprising at least one adhesive layer, the article comprising:
The present invention also relates to an article in which the adhesive layer includes an adhesive comprising the cured reactive silicone adhesive composition of the present invention or a cured product thereof.

The shape of the substrate is a sheet or film, and the shape of the adhesive layer is layered. Preferably, at least a portion of the surface of the substrate adheres to the adhesive layer. The properties of the adhesive material are as described above.

A plurality of the base bodies or the substrates may exist. In this case, the adhesive layer can be present between a plurality of substrates or substrates, and preferably bonds the plurality of substrates or substrates to each other.

The base body or the substrate may be porous or non-porous.

Examples of the porous substrate or porous substrate include textile products such as woven fabrics, nonwoven fabrics, and paper, synthetic resin films and sheets made porous by stretching, and combinations thereof. The fibers may be natural fibers, synthetic fibers, or a mixture thereof.

In the article of the present invention comprising a porous substrate or a porous substrate, the adhesive material of the present invention can be present within the pores of at least a portion of the substrate or substrate. In this case, for example, a porous substrate or substrate such as cloth or paper is impregnated with the composition of the present invention (including impregnation in a heated molten state and cooling), and if necessary, the composition is further heated at a high temperature to harden. By doing so, such articles can be manufactured.

Examples of the non-porous substrate or non-porous substrate include synthetic resin films/sheets, metal foils, and combinations thereof.

In particular, synthetic resin films and sheets are preferred, and examples of the synthetic resin include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol (PVA), polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon. In particular, when heat resistance is required, films of heat-resistant synthetic resins such as polyimide, polyetheretherketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide, polyethersulfone, etc. are suitable. On the other hand, in applications requiring visibility such as display devices, transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, PVA, polycarbonate, polyethylene terephthalate, PEN, or mixtures thereof are suitable.

The thickness of the substrate is not particularly limited, and can be designed to have a desired thickness depending on the application. Furthermore, in order to improve the adhesion between the substrate and the pressure-sensitive adhesive layer, a substrate that has been subjected to primer treatment, corona treatment, etching treatment, or plasma treatment may be used. Furthermore, the surface of the substrate opposite to the surface in contact with the pressure-sensitive adhesive layer may be subjected to surface treatments such as scratch prevention, stain prevention, fingerprint prevention, antiglare, antireflection, and antistatic properties.

A plurality of the adhesive parts or the adhesive layers may exist. By using a plurality of adhesive parts or adhesive layers, various characteristics required for adhesion can be exhibited in a well-balanced manner.

The adhesive component or the adhesive layer is useful as a member of various electronic devices or electrical devices. In particular, the shear storage modulus G' at -20°C of the adhesive component or the adhesive layer is in the range of 0.01 to 1.0 MPa (more preferably in the range of 0.02 to 0.90 MPa, and more preferably in the range of 0.03 to The range of 0.80 MPa is even more preferable, and the range of 0.04 to 0.70 MPa is even more preferable), the adhesive component or the adhesive layer can be used as an elastic adhesive component or an elastic adhesive layer for electronic components. Or it is useful as a member for transducers (including those for sensors, speakers, actuators, and generators).

The adhesive material may be opaque or transparent.

Opaque or low light transmittance adhesive materials are used for film-like or sheet-like members used in sensors, speakers, actuators, etc. where transparency is not required and the parts or layers themselves are required to have a certain degree of stretchability or flexibility. Useful for applications. It is also useful as a sealant or adhesive used in secondary batteries such as lithium ion batteries, or fuel cells.

Transparent to highly transparent adhesives are useful for optical device applications. In this case, it is preferable that the base body or the substrate is a member for an optical device. For example, the substrate can be an optical film such as an image display panel, a touch panel, a polarizing film, a retardation film, a color filter, a viewing angle expansion film, a brightness enhancement film, a reflective sheet, or a front or back protection sheet. . Therefore, the pressure-sensitive adhesive layer is, for example, a surface protection sheet and an optical film, an optical film and a touch panel, a surface protection sheet and an image display panel, a back protection sheet and an image display panel, a surface protection sheet and a touch panel, a touch panel and an image display panel. can be joined.

More specifically, an optical device can be constructed by bonding together two members selected from an image display panel, a touch panel, an optical film, and a front or back protection sheet via at least one adhesive material. . Note that the bonding method and order may be bonded one by one or two at the same time, and there are no restrictions at all. Further, after bonding two optical device constituent members together via the cured reactive silicone adhesive composition of the present invention or a semi-cured product thereof, heating may be further performed at a high temperature from the optical device constituent member side. Such a composition or a semi-cured product thereof can also be cured. By adopting such a method, even optical device constituent members having irregularities can be easily laminated smoothly due to the excellent level difference absorbing performance of the composition of the present invention before curing, or after lamination. It has advantages such as excellent reliability.

The material of the front or back protective sheet is not particularly limited, and examples include glass, (meth)acrylic resin such as polymethyl methacrylate, polycarbonate resin, cycloolefin polymer, acetyl cellulose resin such as triacetyl cellulose, Examples include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; plastics such as acyclic olefin resins such as polypropylene and polyethylene; and mixtures of these plastics.

The surface protection sheet may be one in which a touch panel is integrated, for example, a touch-on-lens (TOL) type or one glass solution (OGS) type. Further, the surface protection sheet may have a printed step portion printed in a frame shape on the peripheral edge thereof.

For example, in the display screen of a mobile phone, a surface protection sheet is generally laminated on a functional film such as a touch panel via an adhesive sheet. A concealing printing part (about 5 μm to 80 μm thick) is attached, and if the adhesive does not fully penetrate into the inside corner of the stepped part formed at the edge of the concealing printing part, air bubbles will remain and the screen will be damaged. Visibility will be reduced. Furthermore, there is a risk that the film member may be bent near the step, resulting in poor appearance, or that residual strain caused by the bending of the film may cause foaming or peeling between the laminated members. The composition of the present invention can fill every corner of the step and adhere without leaving any air bubbles, even if there is a step of about 50 μm to 80 μm, as well as a step of about 5 μm to 20 μm. . Moreover, even if one of the adherends is a flexible film member, by hot-melting the composition of the present invention, it is possible to make the surface smooth and smooth without distortion. It is possible to bond and integrate members without causing distortion or deformation.

The touch panel is not particularly limited, and may be of a resistive type, a capacitance type, an electromagnetic induction type, or a combination thereof. The touch panel preferably includes at least one cover film, a transparent electrode layer such as an ITO or ATO film, or a glass substrate. Note that the touch panel may further include a decorative film or the like.

The image display panel is not particularly limited as long as it displays image information; for example, in the case of a liquid crystal display, it may be a polarizing film, a retardation film, a color filter, a viewing angle expansion film, a brightness enhancement film, or a reflective film. It consists of an optical film such as a sheet, a liquid crystal material, a transparent substrate, and a backlight system (normally, the surface to which the adhesive material is attached to the image display panel is the optical film). , VA method, IPS method, etc., but any method may be used. Further, the image display panel may be an in-cell type in which a touch panel function is built into a TFT-LCD, or an on-cell type in which a touch panel function is built in between a polarizing plate and a glass substrate provided with a color filter. On the other hand, in the case of an organic EL display, the image display panel is composed of an organic EL element substrate or a laminate of an organic EL element substrate and other optical films.

In this case, the article of the present invention is preferably a display, such as a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface conduction electron-emitting device display (SED), or a field emission type display. A display (FED) is more preferred, and a liquid crystal display or an organic EL display is even more preferred.

The image display surface of the display may be flat (plane), or may have a curved surface or curved shape.

The display of the present invention is, for example, a communication device such as a mobile phone or a landline telephone; a computer device such as a tablet terminal, a desktop terminal, or a notebook terminal; a TV; a printer; an ATM (automated teller machine); an in-vehicle monitor or a navigation device. System; Digital camera; Video camera; Medical equipment; PDA (mobile terminal); Watch; Electronic paper; CD, DVD or Blue-ray disc player; Solid-state electronic recording media player such as SSM or HD; Electronic book device; Mobile game Applicable to applications such as play equipment, stationary game equipment, etc.; POS systems; fish finders; automatic ticket vending machines; instrument panels, etc.

On the other hand, the base or the substrate can be a solar cell, a sealing material layer, or a front or back protection sheet. Therefore, the pressure-sensitive adhesive layer can be used, for example, as a surface protection sheet and a solar cell, a back protection sheet and a solar cell, a surface protection sheet and an encapsulant layer, a back protection sheet and an encapsulant layer, or an encapsulant layer. Solar cells can be bonded together.

In this case, the article of the present invention is preferably a solar cell module.

Hereinafter, specific usage examples of the present invention will be further explained.

[Display panel or display member]
Since the cured reactive silicone pressure-sensitive adhesive composition of the present invention or a pressure-sensitive adhesive made of a cured product thereof has pressure-sensitive adhesive properties, it can be used for constructing and utilizing a laminated touch screen or flat panel display, and the specifics thereof. As for the method of use, any known method of using a pressure-sensitive adhesive layer (particularly silicone PSA) can be used without particular limitation.

For example, the adhesive material made of the cured reactive silicone adhesive composition of the present invention or its cured product may be an optically transparent silicone-based pressure-sensitive adhesive disclosed in Japanese translations of PCT publication No. 2014-522436 or PCT publication No. 2013-512326, etc. It can be used as an adhesive film or adhesive layer in the manufacture of display devices such as touch panels. Specifically, the cured product obtained by curing the composition of the present invention can be used without particular limitation as an adhesive layer or adhesive film described in Japanese Patent Publication No. 2013-512326.

As an example, the article of the present invention includes a base material such as a conductive plastic film having a conductive layer formed on one side, and the present invention attached to the side on which the conductive layer is formed or the opposite side thereof. The touch panel may include an adhesive material made of a cured reactive silicone adhesive composition or a cured product thereof. The base material is preferably a sheet-like or film-like base material, such as a resin film or a glass plate. Further, the conductive plastic film may be a resin film or a glass plate, particularly a polyethylene terephthalate film, on one side of which an ITO layer is formed. These are disclosed in PCT International Publication No. 2013-512326 and the like.

In addition, the curable reactive silicone adhesive composition of the present invention or the adhesive material made of the cured product thereof may be used as an adhesive film for a polarizing plate used in the production of display devices such as touch panels, and is disclosed in JP-A No. 2013-065009. It may be used as a pressure-sensitive adhesive layer for bonding between a touch panel and a display module as described in .

Manufacture and structure of laminate FIG. 1 is a sectional view showing a laminate according to an embodiment of the present invention. The laminate 1 according to an embodiment of the present invention includes a first member 20, a second member 21, and a cured reactive silicone adhesive composition of the present invention disposed between the two members 20, 21. An adhesive material 15 made of the cured product is provided. In the laminate 1, two members 20 and 21 are bonded together with an adhesive material 15. These optical members may be transparent or opaque, and one or both members may be a single base material, or may be an independent laminate like a backlight unit. It may also be an optical member. Note that the members constituting the laminate of the present invention generally include a plate-like portion having a planar spread, and the plate-like portion or the member itself may be curved. It may be provided with three-dimensional unevenness derived from the intended use.

The two optical members 20 and 21 can be combined as desired. The two optical members 20 and 21 may be the same or different.

Preferably, members 20, 21 are those commonly used as components of optical displays. More specifically, the members 20 and 21 are optical members, such as lenses (which may be made of resin or glass), optical sheet-like members (color filters, polarizing plates, retardation plates, viewing angle enlarging films, etc.). , brightness enhancement film, reflective sheet, transparent conductive film), optical protective material that may be transparent (transparent protective material (transparent protective film), etc., made of glass, resin, or resin coating layer), front surface It can be a display panel, a touch panel (made of glass or resin), a transparent electrode layer such as an ITO or ATO film. Needless to say, the surface of the display panel or touch panel may further include an optical protective material. Further, the optical member may be a backlight unit itself including a light emitting layer and a display surface (display panel), which will be described later, or a component in which the entire optical member is an independent laminated member or a module in a display device such as a touch panel. The optical member may further include an adhesive layer 15 made of the cured product. That is, the concept of an optical member includes an image display panel, an optical panel, a front panel, a backlight unit, a touch panel unit, etc., which will be described later.

The materials of the members 20 and 21 are not particularly limited as long as they are commonly used in the above applications, but include glass, inorganic optical materials such as indium tin oxide (ITO), polycarbonate resin, Acrylic resin, epoxy resin, polystyrene resin, polyamide resin, polyimide resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol (PVA) resin, polyethylene terephthalate (PET) resin, cyclopolyolefin resin, poly Examples include organic optical materials such as ether ether ketone resin, polyethylene naphthalate (PEN) resin, liquid crystal polyarylate resin, polyamideimide resin, polyether sulfone resin, or mixtures thereof.

In particular, when heat resistance is required, polyimide resin, polyetheretherketone resin, polyethylene naphthalate (PEN) resin, liquid crystal polyarylate resin, polyamideimide resin, polyethersulfone resin, or a mixture thereof may be used.

On the other hand, in applications requiring visibility such as display devices, polypropylene resin, polystyrene resin, polyvinylidene chloride resin, PVA resin, polycarbonate resin, PET resin, PEN resin, or a mixture thereof may be used.

The members 20 and 21 may be subjected to a surface treatment that is commonly applied to constituent members of optical displays. The surface treatment can be, for example, a primer treatment or a corona treatment.

When the two members are different from each other, the two optical members may be separated at the adhesive interface due to, for example, a difference in coefficient of thermal expansion between the two members. However, the curing reactive silicone adhesive composition of the present invention can be heated and melted between parts to follow the gaps and irregularities on the parts, and then cured, and the cured product has flexibility. , the influence of the difference in thermal expansion coefficient can be reduced, and the two mutually different members 20 and 21 can be bonded well. Therefore, the adhesive material of the present invention or a cured product thereof can be suitably used for adhering different members, particularly for adhering organic materials and inorganic materials having a large difference in coefficient of thermal expansion.

Although the laminate 1 shown in FIG. 1 includes two members, the number of members is not particularly limited as long as it includes a plurality of members, especially optical members.

The adhesive material 15 shown in FIG. may have been done. Furthermore, although the adhesive material 15 shown in FIG. It may be formed on the surface 21a opposite to the adhesive surface 21b, or may be formed on both surfaces 20b and 21a.

Hereinafter, a method for manufacturing a laminate according to an embodiment of the present invention will be described.

FIG. 2 is a flowchart showing a method for manufacturing a laminate according to an embodiment of the present invention. A method for producing a laminate according to an embodiment of the present invention includes disposing the curing reactive silicone adhesive composition of the present invention on one or both surfaces of at least one of two members, The method includes a step S1 of arranging and bonding together via a silicone pressure-sensitive adhesive composition, and a curing step S2 of starting a hydrosilylation reaction by heating at a high temperature and curing the composition.

In the above arrangement step S1, the composition of the present invention is arranged on the member using, for example, the above-mentioned coating method. In the above arrangement step S1, the composition of the present invention may be arranged on one surface of one member. In addition, the adhesive material, which is the cured reactive silicone adhesive composition of the present invention or its cured product placed on both sides of the member and is not used for bonding with other optical members, may be used as an adhesive surface such as a release layer or other adhesive material. It may also be used for joining to members.

Moreover, in another embodiment, the composition of the present invention may be placed on one side of each of the two members in the above placement step S1.

In the above embodiments, "one surface" is the surface facing the other optical member.

Furthermore, in another embodiment, in the above placement step S1, the composition of the present invention may also be placed on the other surface located on the opposite side to the above one surface.

FIG. 3 is a conceptual diagram of a method for manufacturing a laminate including a heating and melting process. In the above arrangement step S1, when the member 21 has irregularities and the cured reactive silicone adhesive composition of the present invention is molded into a sheet shape or the like and used as the adhesive material 15, ), the adhesive material 15A made of the cured reactive silicone adhesive composition of the present invention is placed on the member 21 before being heated and melted, and then heated to 80° C. or higher to melt it, and the melt is poured into the recess of the member 21. A process (see FIG. 3(B)) is adopted in which the adhesive material 15B has a smooth surface by molding it into a specific shape, etc. corresponding to the adhesive material 15B, or by filling the gap in the member 21 (not shown). You may. Since the adhesive material of the present invention is heat-meltable, it can be easily molded into a desired shape such as a sheet, and by including this process, it can be used to fill in irregularities and gaps on the member as necessary. It has the advantage that it has excellent adhesive properties and can form a flat adhesive surface if necessary. In particular, even parts that are difficult to adhere to due to their material, unevenness, or gaps can be easily bonded by heating and melting the curing reactive silicone adhesive composition of the present invention. In some cases, it is possible to form an adhesive layer with even higher strength through the curing process described below.

A method for manufacturing a laminate according to an embodiment of the present invention includes disposing the curable reactive silicone adhesive composition of the present invention on one or both surfaces of at least one of two optical members, and The method includes a placement step S1 of bonding together via a curing reactive silicone pressure-sensitive adhesive composition, and a curing step S2 of curing the composition by advancing a hydrosilylation reaction of the composition by heating at a high temperature.

In the above-mentioned curing step S2, a cured product obtained by curing the composition of the present invention is preferably obtained by heating at a high temperature of 150° C. or higher.

Optical Display FIG. 4 is a cross-sectional view of an optical display of one embodiment of an article of the invention. An optical display 200 as an embodiment of the present invention includes the above-described laminate 1 and an image display panel 201.

The laminate 1 and the image display panel 201 are bonded together via an adhesive layer (not shown). This adhesive layer may be composed of the cured reactive silicone pressure-sensitive adhesive composition of the present invention or a cured product thereof.

In the optical display 200 shown in FIG. 4, the second optical member 21 of the laminate 1 is in contact with the adhesive layer. In the optical display 200 shown in FIG. 4, for example, the first optical member 20 of the laminate 1 may be a polarizing film, and the second optical member 21 may be a retardation film. In another embodiment, for example, the first optical member 20 of the laminate 1 may be a polarizing film, and the second optical member 21 may be a surface protection film.

The image display panel 201 is not particularly limited as long as it displays image information; for example, in the case of a liquid crystal display (LCD), a polarizing film, a retardation film, a color filter, a viewing angle expansion film, a luminance Comprised of an optical film such as an improvement film, a reflective sheet, a liquid crystal material, a transparent substrate, and a backlight system (usually, the surface to which the pressure-sensitive adhesive component or pressure-sensitive adhesive layer is attached to the image display panel is an optical film) Depending on the control method of the liquid crystal material, there are STN method, VA method, IPS method, etc., but any method may be used. Further, the image display panel 201 may be an in-cell type in which a touch panel function is built into a TFT-LCD, or an on-cell type in which a touch panel function is built in between a glass substrate provided with a polarizing plate and a color filter. . On the other hand, in the case of an organic EL display, the image display panel 201 is composed of an organic EL element substrate or a laminate of an organic EL element substrate and other optical films.

Optical display 200 may be a cathode ray tube (CRT) display or a flat panel display (FPD). Examples of FPDs include light-receiving display devices such as LCDs and electrochromic displays (ECDs), electroluminescent displays (ELDs) such as organic EL displays and inorganic EL displays, plasma displays (PDPs), and surface conduction electron-emitting devices. Examples include field emission displays (FED) such as displays (SED), and light emitting display devices such as LED displays.

FIG. 5 is a cross-sectional view of an optical display of another embodiment of an article of the invention. An optical display 300A as another embodiment of the present invention includes an image display panel 301, an optical member 20, and a curing reactive silicone adhesive composition of the present invention disposed between the image display panel 301 and the optical member 20. an adhesive layer 15 made of a material or a cured product thereof.

The image display panel 301 may be the same as the image display panel 201 in FIG. 4 .

The optical display 300A, for example, has the optical member 20 disposed on one surface 301a of the image display panel 301 via a curable layer made of the curable reactive silicone adhesive composition of the present invention, which is heated and melted as necessary. After that, the curable layer can be cured by heating at a high temperature.

The optical display according to the embodiment of the article of the present invention shown in FIG. After forming the optical member 20 on the surface 20a, the optical member 20 is placed on one surface 301a of the image display panel 301 via the curable layer, and the curable layer is further cured by heating. .

FIG. 6 is a cross-sectional view of an optical display of another embodiment of an article of the invention. An optical display 300B as another embodiment of the present invention includes an image display panel 301, a touch panel 302, and a cured reactive silicone adhesive composition of the present invention disposed between the image display panel 301 and the touch panel 302. An adhesive layer 15 made of the cured product is provided.

The touch panel 302 is not particularly limited, and may be of a resistive type, a capacitance type, an electromagnetic induction type, or a combination thereof. The touch panel 302 preferably includes at least one cover film, a transparent electrode layer such as an ITO or ATO film, or a glass substrate. Note that the touch panel may further include a decorative film or the like.

In the optical display according to the embodiment of the article of the present invention shown in FIG. Visibility of an optical display can be improved by adhesion or sticking with a cured reactive silicone pressure-sensitive adhesive composition or a cured product thereof.

The curing reactive silicone pressure-sensitive adhesive composition of the present invention has sufficient adhesiveness, can achieve high conformability to irregularities of a member by heating and melting, and has the property of rapidly curing at a high temperature of 150° C. or higher. Therefore, in the optical display of the present invention, the deformation and deterioration of the thermally unstable material is suppressed, and furthermore, the cured product is unlikely to become cloudy or colored even when exposed to high temperature and high humidity, so the optical display The reliability of the system can be improved.

The optical display of an embodiment of an article of the invention further comprises:
further comprising a shield substrate provided on a surface facing the display surface of the front panel and having a surface on which a transparent conductive film is formed,
The display device may have a structure in which the transparent conductive film and the bezel are electrically connected via a conductive material.

For example, in a display device, a shield substrate such as an electromagnetic interference (EMI) substrate having a conductive layer on one side can be further inserted between the display module and the front panel. Since such a shield board has an electromagnetic wave shielding function, it prevents the front panel from malfunctioning due to electromagnetic waves radiated from the display module. Further, on one side of the shield substrate, a conductive layer made of a transparent conductive film such as ITO is formed uniformly or in a mesh shape. In order to set the potential of the conductive layer to GND of the display module, an adhesive member or the like disposed around the outer periphery of the bezel may be formed of a conductive adhesive member such as Ag paste. Note that the bezel of the display module is made of metal and is connected to GND within the display module. Here, by using a conductive material as the adhesive member, the metal bezel and the conductive layer of the shield substrate can be reliably connected to GND, so that a display device with strong electromagnetic wave resistance can be provided.

FIG. 7 is an exploded perspective view of an optical display of another embodiment of an article of the invention. Additionally, FIG. 8 is a partial cross-sectional view showing an optical display of another embodiment of the article of the present invention.

As shown in FIGS. 7 and 8, a display device 400 (optical display) according to the present invention includes a display panel 110 having a display surface 111, a frame portion 121, and an open end 122 inside the frame portion 121. , a bezel 120 that covers the peripheral edge of the display panel 110 on the display surface 111 side with a frame 121, a front panel 130 provided on the display surface 111 side of the display panel 110 with the bezel 120 sandwiched therebetween, and an open end of the bezel 120. A resin member 140 that fills the gap 172 created at the overlapped portion of the bezel 120 and the display surface 111 without any gap in the direction perpendicular to the display surface 111 immediately below the display surface 111 and the front surface. and an OCR 150 filled between the panel 130 and the panel 130. Here, the display surface 111 refers to the entire surface of the display panel 110 on the front panel 130 side.

FIG. 8 shows a structure in which a dam (resin member) 140 is further provided on the bezel 120 and a space 173 between it and the front panel 130 is filled with OCR 150 made of the cured product, a so-called two-stage dam structure. Note that, unlike the illustration, the resin member 140 under the bezel may be only on the upper or lower stage. The display panel 110 is mounted on the backlight unit 171, and the bezel 120 and the backlight unit 171 are fixed by a fitting structure (not shown), thereby forming the display module 170. The entire surface of the display module 170 and the front panel 130 such as a touch panel is bonded together via the OCR 150.

In the embodiment of the article of the present invention shown in FIGS. 7 and 8, the curing reactivity of the present invention is applied to the inner layer of the front panel 130, the OCR 150, the resin member 140 under the bezel (which may be either the upper layer or the lower layer), etc. A silicone adhesive composition or a cured product thereof can be applied. Note that the use is not limited to these applications, and the adhesive material made of the cured reactive silicone adhesive composition of the present invention or its cured product can be used for joining or filling inside each member or between each member shown in FIGS. 7 and 8. can be used.

There are no restrictions on the use of the curing-reactive silicone (organopolysiloxane) composition of the present invention and the cured product obtained by curing it, other than those disclosed above, and the curing-reactive silicone pressure-sensitive adhesive composition of the present invention Adhesive sheets comprising an adhesive material made of a substance or a cured product thereof can be used for television receivers, computer monitors, personal digital assistant monitors, surveillance monitors, video cameras, digital cameras, mobile phones, personal digital assistants, automobiles, etc. For displaying characters, symbols, and images, such as instrument panel displays of various facilities, devices, and equipment, automatic ticket vending machines, automatic teller machines, in-vehicle display devices, and in-vehicle transparent screens. It can be used for various display devices. The surface shape of such a display device may be curved or curved rather than flat, and in addition to various flat panel displays (FPD), curved displays used in automobiles (including electric vehicles), aircraft, etc. Alternatively, a curved transmissive screen is exemplified. Furthermore, these display devices can display icons for executing functions or programs on screens or displays, notification displays such as e-mail programs, car navigation devices, membranes for speakers, audio devices, air conditioners, etc. A touch panel function may be added that can display operation buttons of the device and allows input operations by touching these icons, notification displays, or operation buttons with a finger. Devices include display devices such as CRT displays, liquid crystal displays, plasma displays, organic EL displays, inorganic EL displays, LED displays, surface electrolytic displays (SED), field emission displays (FED), and touch panels using these. Application is possible. In addition, since the adhesive material made of the cured reactive silicone adhesive composition of the present invention or its cured product has excellent adhesive properties and viscoelastic properties, it can be used in transducer members such as membranes for speakers (sensors, speakers, actuators, etc.). In addition to being usable as a film or sheet-like member for use in (and for generators), it can also be used as a sealing layer or adhesive layer for secondary batteries, fuel cells, or solar cell modules.

The adhesive material made of the cured reactive silicone adhesive composition or the cured product thereof of the present invention may be substantially transparent, and can be used without causing problems of poor curing or deterioration of curability, and can be used in various display devices, etc. Vehicle display devices that have excellent adhesion to the base material and have good visibility and operability of displayed content over a long period of time, especially vehicle displays that are equipped with a curved screen or curved display and optionally have a touch panel function. It can be suitably used for devices. For example, JP2017-047767A, JP2014-182335A, JP2014-063064A, JP2013-233852A, etc. disclose vehicle display devices with curved display surfaces. However, the pressure-sensitive adhesive layer of the present invention can be suitably applied or replaced as part or all of the adhesive layer or adhesive layer in which transparency is required in these documents. Furthermore, the curing reactive silicone adhesive composition of the present invention or the adhesive material made of the cured product thereof can be applied to other known curved display devices as well as adhesive layers or adhesive layers that are currently used and require transparency. It goes without saying that the curing reactive silicone adhesive composition of the present invention or the adhesive material made of the cured product thereof can be utilized by adjusting the design of the display device and the thickness of the member using known methods. It is preferable to do so.

In addition, the transparent film-like base material provided with the adhesive material made of the cured reactive silicone adhesive composition of the present invention or its cured product can be used to prevent scratches on the display surface, prevent dirt, prevent fingerprints from attaching, and prevent static electricity. , may be used for purposes such as anti-reflection and anti-peeping purposes.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples in any way.

[Experimental example of liquid composition]
Examples 1 to 3 and Comparative Examples 1 and 2 are experimental examples regarding cured reactive silicone adhesive compositions that are liquid at 25°C, and their composition (parts by mass), viscosity, adhesive strength of cured products, etc. are shown in Table 1. In the table, the ratio of the molar amount of silicon-bonded hydrogen atoms to 1 mole of the total amount of alkenyl groups in the composition is described as "SiH/Vi ratio."

[Experimental example of non-flowable composition]
Examples 4 and 5, and Comparative Example 3 are experimental examples regarding curing reactive silicone adhesive compositions designed to be non-flowable at 25°C and have heat-melting properties (hot-melt properties). Table 2 shows its composition (parts by mass), adhesive strength of uncured product and cured product, etc. In the table, the ratio of the molar amount of silicon-bonded hydrogen atoms to 1 mole of the total amount of alkenyl groups in the composition is described as "SiH/Vi ratio."

The components used in this example are shown below. In each structural formula, Me is a methyl group and Vi is a vinyl group.
The following components were used as component (A).
a-1: ViMe ₂ SiO (SiMe ₂ O) ₄₇₄₅ (SiViMeO) ₂₅ Me ₂ Vi
a-2: ViMe ₂ SiO (SiMe ₂ O) ₈₃₀ SiMe ₂ Vi
The following components were used as component (B).
b-1: Me ₃ SiO (SiMeHO) ₅₀ SiMe ₃
b-2: Me ₃ SiO (SiMe ₂ O) ₂₅ (SiMeHO) ₅₄ SiMe ₃
b-3: Me ₂ HSiO (SiMe ₂ O) ₂₄ SiMe ₃ H
b-4: Me ₃ SiO (SiMe ₂ O) ₃₀ (SiMeHO) ₃₀ SiMe ₃
The following components were used as component (C).
c: Divinyltetramethyldisiloxane solution of platinum (zero-valent) divinyltetramethyldisiloxane complex (platinum metal concentration: 4% by mass).
The following components were used as component (D) and comparative component, respectively.
d: 1,3-bis(diphenylphosphino)propane.
d': The following component was used as the 3,5-dimethyl-1-hexyn-3-ol (E) component.
e-1: (Me ₃ SiO _1/2 ) _0.46 (SiO _4/2 ) _0.54 (HO _1/2 ) _0.05
e-2: (Me ₃ SiO _1/2 ) _0.48 (SiO _4/2 ) _0.52 (HO _1/2 ) _0.04
e-3: (ViMe ₂ SiO _1/2 ) _0.046 (Me ₃ SiO _1/2 ) _0.394 (SiO _4/2 ) _0.56 (HO _1/2 ) _0.05
The following component was used as (F component).
f-1: xylene f-2: toluene

Furthermore, measurements and evaluations in the experimental examples were performed as follows.
[Measurement of viscosity]
"Viscosity (mPa·s)" was measured using a rotational viscometer in accordance with JIS K7117-1.
[Measurement of adhesive strength]
Using a tensile testing machine (RTC-1210 manufactured by Orientech Co., Ltd.), the peeling "adhesive force (gf/inch)" was measured at a tensile speed of 300 mm/min using a 180° peeling test method according to JIS Z0237. Here, the measurement was performed at 25°C.

[Example 1]
Each component of Example 1 shown in Table 1 was mixed uniformly to prepare a curing reactive silicone adhesive composition 1. Mixing was done using a batch mixer at 25°C. Immediately after preparation, the viscosity of the composition at 25°C was measured. Further, after storing the composition at 25°C for 24 hours, the viscosity at 25°C was measured. The results are shown in the columns of "Viscosity of silicone composition <immediately after preparation>" and "Viscosity of silicone composition <after preparation and after storage at 25° C. for 24 hours>" in Table 1, respectively.
As is clear from Table 1, no increase in viscosity was observed over time.

Next, immediately after preparation, cured reactive silicone adhesive composition 1 was applied onto a polyimide film (manufactured by DuPont-Toray Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 μm) using an applicator. The solvent was removed and the material was cured by heating at .degree. C. for 5 minutes. Furthermore, it was stored at 25° C. for 1 day to produce a cured sheet 1-1. Here, the coating amount of the composition was adjusted so that the thickness of the silicone layer after removing the solvent and curing was 50 μm.
The sheet was cut to a width of 20 mm and a length of 300 mm, and the adhesive layer surface was pressed and bonded onto a stainless steel plate (SUS304, 50 x 120 x 2 mm) using a 2 kg rubber roller to create a test piece for measuring adhesive strength. The force was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.

Furthermore, after storing the cured reactive silicone adhesive composition 1 at 25° C. for 24 hours, a cured sheet 1-2 was prepared in the same manner as above, and a test piece for measuring the adhesive force was also prepared, and the adhesive force was measured. It was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>" in Table 1.

There was no major difference in the adhesive strength between the two, and both had good adhesiveness.

[Example 2]
In the same manner as in Example 1, each component of Example 2 shown in Table 1 was mixed uniformly to prepare a curing reactive silicone pressure-sensitive adhesive composition 2. Immediately after preparation, the viscosity of the composition at 25°C was measured. Further, after storing the composition at 25°C for 24 hours, the viscosity at 25°C was measured. The results are shown in the columns of "Viscosity of silicone composition <immediately after preparation>" and "Viscosity of silicone composition <after preparation and after storage at 25° C. for 24 hours>" in Table 1, respectively.
As is clear from Table 1, almost no increase in viscosity was observed over time.

Next, in the same manner as in Example 1, a cured sheet 2-1 was prepared and its adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.

Furthermore, in the same manner as in Example 1, a cured sheet 2-2 was prepared and its adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>" in Table 1.

There was no major difference in the adhesive strength between the two, and both had good adhesiveness.

[Example 3]
In the same manner as in Example 1, each component of Example 3 shown in Table 1 was mixed uniformly to prepare a curing reactive silicone adhesive composition 3. Immediately after preparation, the viscosity of the composition at 25°C was measured. Further, after storing the composition at 25°C for 24 hours, the viscosity at 25°C was measured. The results are shown in the columns of "Viscosity of silicone composition <immediately after preparation>" and "Viscosity of silicone composition <after preparation and after storage at 25° C. for 24 hours>" in Table 1, respectively.
As is clear from Table 1, no increase in viscosity was observed over time.

Next, immediately after preparing the curing reactive silicone adhesive composition 3, toluene (solvent) was further added (5 parts by mass to 100 parts of the composition) and mixed uniformly. It was applied onto a film (manufactured by DuPont-Toray Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 μm) using an applicator, and was heated at 150° C. for 5 minutes to remove the solvent and cure. Furthermore, it was stored at 25° C. for 1 day to prepare a cured sheet 3-1. Here, the coating amount of the composition was adjusted so that the thickness of the silicone layer after removing the solvent and curing was 50 μm.
The sheet was cut to a width of 20 mm and a length of 300 mm, and the adhesive layer surface was pressed and bonded onto a stainless steel plate (SUS304, 50 x 120 x 2 mm) using a 2 kg rubber roller to create a test piece for measuring adhesive strength. The force was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.

Furthermore, after storing the cured reactive silicone adhesive composition 3 at 25°C for 24 hours, a cured sheet 3-2 was prepared in the same manner as above, and a test piece for measuring the adhesive force was also prepared, and the adhesive force was measured. It was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>" in Table 1.

No difference was observed in the adhesive strength between the two, and the adhesive strength was suitable for use as a protective material.

[Comparative example 1]
In the same manner as in Example 1, the components shown in Table 1 were uniformly mixed to prepare Comparative Silicone Composition 1. Immediately after preparation, the viscosity of the composition at 25°C was measured. The results are shown in the column "Viscosity of silicone composition (immediately after preparation)" in Table 1.

Further, in the same manner as in Example 1, a comparative cured sheet 1-1 was prepared and its adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.

On the other hand, when Comparative Silicone Composition 1 was stored at 25° C. for 24 hours, the entire sample gelled, making it impossible to measure viscosity or adhesive strength.

[Comparative example 2]
In the same manner as in Example 3, the components shown in Table 1 were uniformly mixed to prepare Comparative Silicone Composition 2. Immediately after preparation, the viscosity of the composition at 25°C was measured. The results are shown in the column "Viscosity of silicone composition (immediately after preparation)" in Table 1.

In addition, in the same manner as in Example 3, a comparative cured sheet 2-1 was prepared and its adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 1.

On the other hand, when Comparative Silicone Composition 2 was stored at 25°C for 24 hours, the entire sample gelled, making it impossible to measure viscosity or adhesive strength.

[Example 4]
Each component of Example 4 shown in Table 2 was mixed uniformly. The mixing was carried out by heating and stirring for 10 minutes at 80° C. and 100 rpm using a Laboplast Mill (manufactured by Toyo Seiki). The rotational torque during mixing showed a constant value after about 1 minute and did not change thereafter. The mixture was taken out and cooled to prepare a cured reactive silicone adhesive composition 4.

The cured reactive silicone adhesive composition 4 immediately after preparation was coated with a polyimide film (manufactured by DuPont-Toray Co., Ltd., product name Kapton (registered trademark) 100H, thickness 25 μm) and a release film (manufactured by Nipper Co., Ltd., FSC-6). Using scissors and a 200 μm thick polyethylene terephthalate film as a spacer, press molding was performed at 70° C. to prepare an uncured sheet 4-1 with a thickness of 200 μm.
The sheet could be reprocessed, including thickness adjustment, by heating it to 70°C.
The sheet was cut to a width of 20 mm and a length of 300 mm, the release film was separated to expose the adhesive surface, and the adhesive layer surface was pressed and bonded onto a stainless steel plate (SUS304, 50 x 120 x 2 mm) using a 2 kg rubber roller. A test piece for measuring adhesive strength was prepared, and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of uncured sheet <uncured sheet prepared immediately after composition preparation>" in Table 2.

Next, the uncured sheet 4-1 was heated and cured at 150° C. for 5 minutes to produce a cured sheet 4-1. This was cut into 20 mm width and 300 mm length, the release film was separated to expose the adhesive surface, and the adhesive layer surface was pressed and bonded onto a stainless steel plate (SUS304, 50 x 120 x 2 mm) using a 2 kg rubber roller. A test piece for measuring adhesive force was prepared, and the adhesive force was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 2.

On the other hand, after storing the cured reactive silicone adhesive composition 4 at 25° C. for 24 hours, an uncured sheet 4-2 was prepared in the same manner as above.
The sheet could be reprocessed, including thickness adjustment, by heating it to 70°C.
Next, the uncured sheet 4-2 was heated and cured at 150° C. for 5 minutes to produce a cured sheet 4-2. This was cut into 20 mm width and 300 mm length, the release film was separated to expose the adhesive surface, and the adhesive layer surface was pressed and bonded onto a stainless steel plate (SUS304, 50 x 120 x 2 mm) using a 2 kg rubber roller. A test piece for measuring adhesive strength was prepared, and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>" in Table 2.

There was no difference in adhesive strength between cured sheet 4-1 and cured sheet 4-2, and both had good adhesive strength.

[Example 5]
Similarly to Example 4, each component of Example 5 shown in Table 2 was mixed uniformly. The rotational torque during mixing showed a constant value after about 1 minute and did not change thereafter. The mixture was taken out and cooled to prepare a cured reactive silicone adhesive composition 5.

In the same manner as in Example 4, an uncured sheet 5-1 having a thickness of 200 μm was prepared using the cured reactive silicone adhesive composition 5.
The sheet could be reprocessed, including thickness adjustment, by heating it to 70°C.
In the same manner as in Example 4, the adhesive strength of uncured sheet 5-1 was measured. The results are shown in the column of "Adhesive strength of uncured sheet <uncured sheet prepared immediately after composition preparation>" in Table 2.
Next, in the same manner as in Example 4, the uncured sheet 5-1 was heated and cured at 150° C. for 5 minutes to produce a cured sheet 5-1, and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared immediately after composition preparation>" in Table 2.

On the other hand, similarly to Example 4, after storing the cured reactive silicone adhesive composition 5 at 25° C. for 24 hours, an uncured sheet 5-2 was prepared in the same manner as above.
The sheet could be reprocessed, including thickness adjustment, by heating it to 70°C.
Next, in the same manner as in Example 4, the uncured sheet 5-2 was heated and cured at 150° C. for 5 minutes to produce a cured sheet 5-2, and the adhesive strength was measured. The results are shown in the column of "Adhesive strength of cured sheet <cured sheet prepared after composition preparation and storage at 25° C. for 24 hours>" in Table 2.

There was no difference in adhesive strength between cured sheet 5-1 and cured sheet 5-2, and both had good adhesive strength.

[Comparative example 3]
In order to uniformly mix each component shown in Table 2, we used Labo Plast Mill (manufactured by Toyo Seiki) and heated and stirred at 80°C and 100 rpm. It was not possible to obtain a silicone composition with the following properties.

[Summary]
As shown in Examples 1 to 3, the curing reactive silicone adhesive compositions 1 to 3 (compositions 1 and 2: solvent type, composition 3: solventless type) of the present invention maintain their properties even after long-term storage. The viscosity did not change, and the adhesive strength of the cured sheet obtained by curing the composition immediately after production/after storage was also almost the same. Although Examples 1 and 2 differed in the amount of the phosphorus-based hydrosilylation reaction retarder, sufficient technical effects were achieved even with a small amount (Example 2). On the other hand, in Comparative Examples 1 and 2 lacking component (D), even though they had similar compositions to those in the examples, they gelled after storage, resulting in a one-component liquid curing reaction with excellent storage stability and adhesive properties. It was not possible to obtain a silicone pressure-sensitive adhesive composition.

As shown in Examples 4 and 5, from the cured reactive silicone adhesive compositions 4 and 5 of the present invention, uncured sheets that can be used as non-flowable and heat-melting adhesives can be obtained, and The adhesive strength of the cured sheet obtained by curing the composition immediately after production/after storage was also approximately the same. On the other hand, from Comparative Example 3 lacking component (D), it was not possible to obtain an uncured sheet usable as a non-flowable and heat-melting adhesive.

Claims (16)

(A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule;
(B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule;
(C) a catalyst for hydrosilylation reaction, and
(D) phosphorus-containing hydrosilylation reaction retardant (C) An amount in a range of 0.30 to 10 mol per mol of metal atom in component ;
(E) A siloxane unit (M unit) represented by R ₃ SiO _1/2 (in the formula, R independently represents a monovalent organic group) and a siloxane represented by SiO _4/2 in the molecule Organopolysiloxane resin containing unit (Q unit) 55% to 90% by mass of the total mass of component (A), component (B), and component (E)
including;
The content of component (B) is such that the silicon-bonded hydrogen atoms in component (B) are 0.5 mole or more per mole of all aliphatic unsaturated carbon-carbon bonds in the composition. ,
A cure-reactive silicone that is tacky in the pre-cure state, non-flowing at 25°C, and has a softening point between 25°C and 150°C, and is a one-component or single composition. Adhesive composition. The phosphorus-containing hydrosilylation reaction retarder of component (D) is selected from the group consisting of phosphine compounds, phosphoric acid compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorous acid compounds, and phosphonous acid compounds. The curing reactive silicone pressure-sensitive adhesive composition according to claim 1, which is at least one selected from the group consisting of: Component (D) is diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, tripropylphosphine, dicyclohexylphenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1 ,2-bis(diphenylphosphino)propane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 2,3-bis(diphenylphosphino)butane, 1,5 -Bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, bis(2-diphenylphosphinoethyl)phenylphosphinebis(diphenylphosphino)acetylene, 1,1-bis(diphenylphosphino) Ethylene, 1,2-bis(diphenylphosphino)ethylene, 1,1-bis(diphenylphosphino)ferrocene, 1,3-bis(dicyclohexylphosphino)propane, 1,2-bis(dimethylphosphino)ethane, The curing reactivity according to claim 1 or 2, which is at least one phosphine compound selected from the group consisting of 1,2-bis(dimethylphosphino)benzene and 1,2-bis(diphenylphosphino)benzene. Silicone adhesive composition. At least a part of component (E) has (Alk)R' ₂ SiO _1/2 in the molecule (wherein Alk independently represents an aliphatic unsaturated carbon-carbon bond-containing group, and R' each Curing reactivity containing at least a siloxane unit (M unit) represented by (independently representing an aliphatic unsaturated carbon-carbon bond-free group) and a siloxane unit (Q unit) represented by SiO _4/2 The curable reactive silicone pressure-sensitive adhesive composition according to claim 1 , which is an organopolysiloxane resin. An adhesive layer with a thickness of 200 μm obtained by curing the composition was attached to a SUS plate, and the adhesive strength was measured at a tensile rate of 300 mm/min using a 180° peel test method according to JIS Z0237. , 0.1 gf/inch or more, the curing reactive silicone pressure-sensitive adhesive composition according to claim 1 . A member, component, or sheet comprising at least the cured reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 5 . A heat-melting adhesive comprising the curing reactive silicone adhesive composition according to any one of claims 1 to 5 . A cured product of the curing reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 5 . Claim 8 , comprising the step of molding the curing reactive silicone adhesive composition according to any one of Claims 1 to 5 at a temperature of less than 150°C, and then heating it to 150°C or higher to cure it. A method for producing the cured product described above. An adhesive material comprising a cured product of the curing reactive silicone adhesive composition according to any one of claims 1 to 5 . A laminate comprising a layer or member made of the curing reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 5 . A laminate comprising a layer or member made of a cured product of the cured reactive silicone pressure-sensitive adhesive composition according to any one of claims 1 to 5 . The laminate according to claim 11 or 12 , wherein at least a portion thereof includes a sheet-like member provided with a release layer. The laminate according to claim 11 or 12 , which is at least one selected from display devices, electronic components, and solar cell modules. Any one of claims 11 to 14 , comprising a step of heating the cured reactive silicone adhesive composition according to any one of claims 1 to 5 to 80° C. or higher to melt it, and molding or filling the melt. A method for producing a laminate according to item 1. A step of sandwiching and laminating the curing reactive silicone adhesive composition or a cured product thereof according to any one of claims 1 to 5 between members, and the curing reactive silicone adhesive composition or a cured product thereof. The method for manufacturing a laminate according to any one of claims 11 to 14 , comprising the step of crimping the member.

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