KR102320575B1 - Silicone adhesive composition having excellent substrate adhesion, and adhesive product - Google Patents

Abstract

Provided are a silicone pressure-sensitive adhesive composition and a pressure-sensitive adhesive article capable of improving adhesion to a substrate by one-time coating. The silicone adhesive composition containing the following (A)-(F) component. (A) at least two alkenyl group-containing containing organopolysiloxane ^{_{(B) R 2 3 SiO 1}} /2 units and SiO _4/2 units having an organic group, and (R _{² 3} SiO ^_1/2 units) in one molecule, / (SiO _{4 /2} unit) polyorganosiloxane having a molar ratio of 0.6 to 1.0 (C) polyorganohydrogensiloxane having at least three Si-H groups in one molecule, (D) a platinum group metal catalyst, ( E) A silicon compound containing 0.15 mol or more of an alkenyl group in 100 g of the compound (F) having one or more repeating units represented by formula (3) and one or more Si-H groups in one molecule.

Description

A silicone pressure-sensitive adhesive composition and an adhesive article having excellent adhesion to a substrate {SILICONE ADHESIVE COMPOSITION HAVING EXCELLENT SUBSTRATE ADHESION, AND ADHESIVE PRODUCT}

The present invention relates to a silicone pressure-sensitive adhesive having improved adhesion to a substrate and an adhesive article.

Adhesives are a kind of adhesive, and are often used in the form of adhesive tapes or adhesive labels that are cured by coating the adhesive on a substrate, and are typical of articles using adhesives that we usually see. These articles have a wide range of uses, such as being used for labels for identifying articles, used for packing luggage, or linking a plurality of articles together.

There are several types of base materials for constituting the pressure-sensitive adhesive, and they are broadly classified into rubber-based, acrylic-based, silicone-based, and the like. A rubber-based pressure-sensitive adhesive is a general-purpose base material that has been used for a long time, and is inexpensive and used in products such as general-purpose tapes. The acrylic pressure-sensitive adhesive is used based on polyacrylate, and its chemical properties are superior to that of the rubber-based adhesive, so it can be applied to adhesive products with higher functionality than rubber-based adhesives. Silicone pressure-sensitive adhesives are made of high-viscosity raw silicone rubber (gum) and silicone resin, and have various excellent characteristics in that the main chain has a large number of siloxane bonds. Specifically, heat resistance, cold resistance, weather resistance, chemical resistance, electrical insulation, etc. can be heard

Silicone pressure-sensitive adhesives are used in industrial high-performance tapes such as heat-resistant tapes, process masking tapes, and flame-retardant mica tapes by taking advantage of the excellent properties as described above, where they can exhibit their properties even in harsh environments is being used in However, in recent years, the demand for silicone pressure-sensitive adhesives is rapidly expanding, and what is becoming a factor is the expansion of the product market employing a touch panel mounted on a smartphone or tablet terminal. In most cases, the touch panel is directly manipulated with a human finger, and thus a screen protection film is bonded and used to prevent contamination or damage to the display. Most of the silicone adhesives used for the adhesive layer of this screen protection film are silicone adhesives, and this utilizes the characteristics of the wettability to the to-be-adhered body excellent in a silicone adhesive, and reworkability.

The base material used for a screen protection film is a film made from a plastic, and polyester films, such as PET which have transparency, are often used. However, it is said that a plastic film has poor adhesiveness with an adhesive compared with a paper base material. It is considered that this is because the anchor effect of the pressure-sensitive adhesive penetrating into the substrate is weaker than that of paper having a flat surface and large irregularities on the plastic film side. If the adhesiveness is poor, problems such as adhesion of ink to other papers when rolled up into a roll or the transfer of an adhesive layer to the adherend when peeled off after time elapses after sticking to an adherend may occur.

In the past, various measures have been taken to improve this adhesion, and there are methods such as using a substrate with good adhesion or corona-treating the substrate. Moreover, a primer treatment is also a widely performed method, and development is advancing also about the primer composition for silicone adhesives (refer patent documents 1-3). Primer treatment is very effective, but the biggest drawback is that the coating process is increased by one, and cost or productivity is a problem. As an effective countermeasure, the method of adding the component which improves adhesiveness to a silicone adhesive and ensuring adhesiveness by one-time coating is considered. Although such an additive also exists (refer patent documents 4-6), the further adhesive improvement is calculated|required. Moreover, although patent document 7 describes about the additive which adhere|attaches selectively to an organic resin, the object is a silicone rubber composition, and it does not mention even a silicone adhesive.

Japanese Special Air Force Hei 6-39584 Gazette Japanese Patent Application Laid-Open No. 7-3215 Japanese Patent Laid-Open No. 2012-149240 Japanese Patent Application Laid-Open No. 2003-105089 Japanese Patent No. 3232004 Publication Japanese Patent Publication No. 2010-500462 Japanese Patent No. 3324166

Therefore, an object of the present invention is to provide a silicone pressure-sensitive adhesive composition and a pressure-sensitive adhesive article capable of improving adhesion to a substrate by one coating.

As a result of earnest examination in order to achieve the said object, this inventor found out that the silicone adhesive composition which adhesiveness with a base material improves by adding the adhesion improver component which has a specific structure can be obtained, and came to achieve this invention .

Accordingly, the present invention provides the following silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive article.

[I]. The silicone adhesive composition containing the following (A)-(F) component.

(A) an organopolysiloxane represented by the following average composition formula (1), having at least two alkenyl group-containing organic groups in one molecule, and containing 0.0007 to 0.05 moles of alkenyl groups in 100 g: 100 to 40 parts by mass;

(Wherein, R ¹ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, and ^{at least two of R 1} includes an alkenyl group-containing organic group having 2 to 10 carbon atoms. a is an integer of 2 or more, b is An integer greater than or equal to 1, c is an integer greater than or equal to 0, d is an integer greater than or equal to 0, and 50≤a+b+c+d≤15,000.)

^{_{(B) R 2 3 SiO 1}} /2 units (wherein, R ² represents an alkenyl group of 1 to 10 carbon atoms in a monovalent hydrocarbon group or having 2 to 6 carbon atoms that does not have an aliphatic unsaturated bond independently.) And SiO _{4 / 2} contains the units and (R _{² 3} SiO ^_1/2 units) / the organopolysiloxane (SiO _4/2 units) molar ratio of 0.5 to 1.0 represented by the following: 60 to 0 parts by weight,

(C) Organohydrogenpolysiloxane represented by the following average compositional formula (2) and having at least three Si-H groups in one molecule: Si-H groups in molar ratio with respect to the alkenyl groups of components (A) and (B) An amount that becomes 0.2 to 15 with

R ³ _e H _f SiO _(4-ef)/2 (2)

(Wherein, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e>0, f>0, and 0<e+f≤3.)

(D) Platinum group metal catalyst for curing by hydrosilylation addition of the alkenyl group of components (A) and (B) and the Si-H group of (B): Amount of metal with respect to the total amount of components (A) to (C) 1 to 500 ppm as

(E) a compound having one or more repeating units represented by the following formula (3) and one or more Si-H groups in one molecule: 0.01 to 10 parts by mass based on the total amount of the components (A) to (C);

[Wherein, R ⁴ to R ¹¹ are the same or different kinds of hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and X is the following formula (4)

(Wherein, R ¹² to R ¹³ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and g is an integer of 1 or more.)

It is selected from the divalent organic group represented by, Y is independently a C1-C6 hydrocarbon group, and may have an ether group in the structure.]

(F) Silicon compound containing 0.15 mol or more alkenyl group in 100 g: 0.01-10 mass parts with respect to the total amount of said (A)-(C) component

[II]. A pressure-sensitive adhesive article comprising a substrate and an adhesive layer formed on at least one side of the substrate, wherein the pressure-sensitive adhesive layer is obtained by coating and curing the silicone pressure-sensitive adhesive composition on at least one side of the substrate.

When the silicone pressure-sensitive adhesive composition obtained by the present invention is applied to a base material and used, an adhesive article having good adhesion to the base material can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[(A) component]

(A) Organopolysiloxane represented by the following average compositional formula (1), having at least two alkenyl group-containing organic groups in one molecule, and containing 0.0007 to 0.05 moles of alkenyl groups in 100 g: 100 to 40 parts by mass.

(Wherein, R ¹ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, and ^{at least two of R 1} includes an alkenyl group-containing organic group having 2 to 10 carbon atoms. a is an integer of 2 or more, b is An integer greater than or equal to 1, c is an integer greater than or equal to 0, d is an integer greater than or equal to 0, and 50≤a+b+c+d≤15,000.)

R ¹ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, and ^{at least two of R 1} includes an alkenyl group-containing organic group having 2 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, and an aryl group such as a phenyl group, and a hydrogen atom bonded to a carbon atom of these groups A part or all of may be substituted with a halogen atom or another group, and a trifluoromethyl group, 3,3,3-trifluoropropyl group, etc. are illustrated as a substituent. Among these, a saturated aliphatic group or an aromatic group is preferable, and a methyl group and a phenyl group are preferable.

The alkenyl group-containing organic group preferably has 2 to 10 carbon atoms, for example, an alkenyl group such as a vinyl group, an allyl group, a hexenyl group and an octenyl group, an acryloylpropyl group, an acryloylmethyl group, and a methacryloyl group. and alkenyloxyalkyl groups such as acryloylalkyl groups such as propyl group, cycloalkenylalkyl groups such as methacryloylalkyl groups and cyclohexenylethyl groups, and vinyloxypropyl groups. Among them, a vinyl group is preferable.

The amount of the alkenyl group contained in (A) is 0.0007 to 0.05 mol in 100 g of organopolysiloxane, preferably 0.001 to 0.04 mol, and more preferably 0.001 to 0.03 mol. When smaller than 0.0007 mol, crosslinking density becomes small and cohesive failure of an adhesive layer may arise, and when larger than 0.05 mol, an adhesive layer becomes hard and appropriate adhesive force and adhesiveness may not be obtained.

a is an integer greater than or equal to 2, b is an integer greater than or equal to 1, c is an integer greater than or equal to 0, and d is an integer greater than or equal to 0, 50≤a+b+c+d≤15,000, 200≤a+b+c+d≤12,000 desirable. If a+b+c+d is less than 50, there is a fear that the reactivity may decrease due to too many crosslinking points, and if it is larger than 15,000, the viscosity of the composition becomes very high, so there is a risk of deterioration in workability such as difficulty in stirring and mixing.

Component (A) is usually produced by ring-opening polymerization of cyclic low-molecular siloxane such as octamethylcyclotetrasiloxane using a catalyst. It is preferable to use a product obtained by distillation while passing an inert gas through it.

(A) Although what is represented by the following general formula as a component is mentioned, It is not limited to these.

R ^1-1 R ^1-2 ₂ SiO(R ^1-2 ₂ SiO) _p SiR ^1-2 ₂ R ^1-1

R ^1-1 R ^1-2 ₂ SiO(R ^1-2 ₂ SiO) _p (R ^1-1 R ^1-2 SiO) _q SiR ^1-2 ₂ R ^1-1

R ^1-2 ₃ SiO(R ^1-2 ₂ SiO) _p (R ^1-1 R ^1-2 SiO) _q SiR ^1-2 ₃

R ^1-1 ₃ SiO(R ^1-2 ₂ SiO) _p (R ^1-1 R ^1-2 SiO) _q SiR ^1-1 ₃

R ^1-1 R ^1-2 ₂ SiO(R ^1-2 ₂ SiO) _p (R ^1-1 R ^1-2 SiO) _q SiR ^1-2 ₂ R ^1-1

(Wherein, R ^1-1 is an organic group containing the same or different types of alkenyl groups, R ^1-2 is the same or different types of monovalent hydrocarbon groups having 1 to 10 carbon atoms, and p≥50 and q≥1 (provided that , (R ^1-1 R ^1-2 SiO) _q ^{≥ 2 when R 1-1} is not present in the molecule other than q).)

Examples of R ^1-1 and R ^1-2 include those exemplified by ^{R 1 above.} Moreover, 50≤p≤15,000 is preferable, 1≤q≤1,000 is preferable, and 2≤q≤1,000 is more preferable.

Although what is represented by the following general formula as a more specific (A) component is mentioned, It is not limited to these. In addition, Me, Vi, and Ph in a following formula represent a methyl group, a vinyl group, and a phenyl group, respectively.

[(B) component]

R _{² 3} SiO ^_1/2 units (wherein, R ² is a monovalent group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond independently represents an alkenyl group of a hydrocarbon group or a carbon number of 2-6.), And SiO _4/2 units containing ^{_{and, (R 2 3 SiO 1/}} 2 units) _/ (SiO _4/2 units), the organo polysiloxane is a molar ratio of 0.5 to 1.0 represented by the. When this molar ratio is less than 0.5, there exists a possibility that adhesive force and adhesiveness may fall, and when it exceeds 1.0, there exists a possibility that adhesive force and holding force may fall. In addition, the molar ratio is preferably 0.6 to 0.9.

R ² independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms which does not have an aliphatic unsaturated bond, and as the monovalent hydrocarbon group having 1 to 10 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group C6-C10 aryl groups, such as a C2-C6 alkyl group, a phenyl group, and a tolyl group, are preferable. As a C2-C6 alkenyl group, a vinyl group, an allyl group, a butenyl group, etc. are preferable.

Component (B) is R ² other than the silanol group and being optionally includes an alkoxy group of the hydrolyzable, the content of (B) for a total of 0.01 ~ 4.0% by mass is preferable, and 0.05 to 3.5% by mass of the mass of the component more preferably. When the said content is less than 0.01 mass %, there exists a possibility that the cohesive force of an adhesive may become low, and when more than 4.0 mass %, there exists a possibility that the adhesiveness of an adhesive may fall. A methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a phenoxy group etc. are mentioned as an alkoxy group, When using, a methoxy group is preferable.

(B) A component may use 2 or more types together. In addition it is also possible to contain the R ^{₂ 2} SiO ^_3/2 units, R ^₂ SiO _^2/2 units within the scope of not impairing the advantages of the present invention in (B).

(B) In catalyst presence, you may make it condensation-react and you may obtain a component. This is an operation in which the hydrolyzable groups present on the surface are reacted, and effects such as improvement of adhesive strength can be expected. What is necessary is just to make it react under room temperature - reflux using an alkaline catalyst, and just to neutralize if necessary.

Examples of the alkaline catalyst include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate salts such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal alkoxides such as sodium methoxide and potassium butoxide; organometals such as butyllithium; potassium silanolate; Although nitrogen compounds, such as ammonia gas, aqueous ammonia, methylamine, trimethylamine, and triethylamine, etc. are mentioned, Ammonia gas or aqueous ammonia is preferable. The temperature of the condensation reaction may be carried out from room temperature to the reflux temperature of the organic solvent. Although the reaction time is not particularly limited, it is 0.5 to 20 hours, preferably 1 to 16 hours. Moreover, you may add the neutralizing agent which neutralizes an alkaline catalyst as needed after completion|finish of reaction. Examples of the neutralizing agent include acid gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octylic acid, and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid. When ammonia gas or aqueous ammonia or an amine compound having a low boiling point is used as the alkaline catalyst, an inert gas such as nitrogen may be passed through the catalyst to be distilled off.

(A) The compounding quantity of 100-40 mass parts and (B) component is 60-0 mass parts, and (B)component may not be contained as for the compounding quantity of (A) component. (A) and (B) The sum total of a component is 100 mass parts. (A), the compounding mass ratio of (B) component is (A)/(B)=100/0-40/60, and 100/0-70/30 is preferable at the point of the adhesive force at the time of using with a film or a tape etc. and 100/0 to 80/20 are more preferable, and 100/0 to 90/10 are still more preferable. (B) When the ratio of a component exceeds 60, adhesiveness may worsen.

[(C)component]

The following average composition formula (2)

R ³ _e H _f SiO _(4-ef)/2 (2)

(Wherein, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e>0, f>0, and 0<e+f≤3.)

It is represented by, and has at least three Si-H groups in one molecule organohydrogenpolysiloxane.

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for R ³ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an allyl group, a hexenyl group, an octenyl group, etc. Aryl groups, such as an alkenyl group of and a phenyl group, etc. are mentioned. In addition, some or all of the hydrogen atoms couple|bonded with the carbon atom of these groups may be substituted by the halogen atom or another group, and a trifluoromethyl group, 3,3,3-trifluoropropyl group, etc. are illustrated. Among these, a saturated aliphatic group or an aromatic group is preferable, and a methyl group and a phenyl group are more preferable. In the average composition formula (2), e>0, f>0, and 0<e+f≤3.

(C) Although the thing of following General formula (8) can be illustrated as a component, it is not limited to this.

R²⁵ ₃Si-O-(R²⁶ ₂Si-O)_t-(R²⁷HSi-O)_u-SiR²⁸ ₃ (8)

(Wherein, R ²⁵ and R ²⁸ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ²⁶ and R ²⁷ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, and t is 0≤t≤100, and u is 3≤u≤80)

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for R ²⁶ and R ²⁷ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an allyl group, a hexenyl group, an alkenyl group, such as an octenyl group, and an aryl group, such as a phenyl group, etc. are mentioned. Further, part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, and examples of the substituent include a trifluoromethyl group and a 3,3,3-trifluoropropyl group. As R ²⁶ and R ²⁷ , a saturated aliphatic group or an aromatic group is preferable, and a methyl group or a phenyl group is more preferable. R ²⁵ and R ²⁸ are a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for R ²⁵ and R ²⁸ include the same ones as described above, t is 0≤t≤100, 0≤u≤80 or 0<u≤80 is preferable, and u is 3≤u≤80, preferably 5≤u≤70.

t in the general formula (8) is an integer satisfying 0 ≤ t ≤ 100, preferably 0 ≤ t ≤ 80 or 0 < t ≤ 80. u in the general formula (8) is an integer satisfying 3≤u≤80, preferably 4≤u≤70.

Component (C) is usually produced by ring-opening polymerization of cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane and siloxane containing Si-H such as tetramethylcyclotetrasiloxane using an acid catalyst, after polymerization Since it contains the cyclic low molecular weight siloxane as a raw material, it is preferable to use what was distilled off while passing an inert gas through the reaction product under heating and reduced pressure.

(C) Although what is shown below as a thing showing the specific structure of a component, etc. are mentioned, It is not limited to these. In addition, Me in the following formula represents a methyl group, respectively.

The compounding quantity of the component of (C) is an quantity from which the Si-H group becomes 0.2-15 in molar ratio (Si-H group/alkenyl group) with respect to the total alkenyl group of (A) and (B) component, 0.5-10 It is preferable to mix it so that it may become a range. If it is less than 0.2, a crosslinking density may become low, and there exists a possibility that cohesive force and holding force may become low by this. On the other hand, when it exceeds 15, crosslinking density becomes high and moderate adhesive force and adhesiveness may not be acquired.

[(D)component]

(D)component is a platinum group metal type catalyst for carrying out hydrosilylation addition of the alkenyl group of (A), (B) component, and Si-H group of (B), and hardening. Examples of the central metal of this catalyst include platinum, palladium, iridium, rhodium, osmium, and ruthenium, and among them, platinum is preferable. Examples of the platinum catalyst include chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and a reaction product of chloroplatinic acid and vinyl group-containing siloxane.

(D) The compounding quantity of component is 1-500 ppm as a metal amount with respect to the total amount of said (A)-(C)component, and 2-450 ppm is preferable. If it is less than 1 ppm, reaction is slow, and there exists a possibility that various characteristics of adhesive force and holding power may not be exhibited by becoming hardening inadequate, and when it exceeds 500 ppm, the softness|flexibility of hardened|cured material may become insufficient.

[(E) component]

(E) A compound having one or more repeating units represented by the following formula (3) and one or more Si—H groups in one molecule.

[Wherein, R ⁴ to R ¹¹ are the same or different kinds of hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and X is the following formula (4)

(Wherein, R ¹² to R ¹³ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and g is an integer of 1 or more.)

It is selected from the divalent organic group represented by, Y is independently a C1-C6 hydrocarbon group, and may have an ether group in the structure.]

In Formula (3), R ⁴ to R ¹¹ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine and bromine, and examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Especially, a hydrogen atom and a C1-C6 hydrocarbon group are preferable, and a hydrogen atom and a methyl group are more preferable.

X is a divalent organic group selected from Formula (4), and R ¹² to R ¹³ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine and bromine, and examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. In these, a hydrogen atom and a C1-C6 hydrocarbon group are preferable, and a hydrogen atom and a methyl group are especially preferable. g is an integer of 1 or more, Preferably it is 1-8, More preferably, it is 1-5. When g is larger than 8, the adhesiveness with a base material may worsen because the alkyl group which occupies in a repeating unit increases.

Y is independently a C1-C6 hydrocarbon group, and may have an ether group in the structure. Examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include the following.

Moreover, the ether group may be included in a molecule|numerator, and the following are mentioned.

Examples of the specific structure of the formula (3) include those shown below, but are not limited thereto. In addition, Me in a following formula represents a methyl group.

As the group containing a Si-H group, for example, a compound having at least two Si-H groups in one molecule represented by the average composition formula (9) described later, specifically, a group in which at least one hydrogen atom has been removed from the following compound (provided that , having at least one Si—H group). (E) The component should just have the group containing a Si-H group at the molecular terminal.

(E) Although the thing shown below is mentioned as a component, for example, It is not limited to these. Z1 and Z2 are 0-10, and 0-4 are preferable.

(E) Component is a base material adhesion improving agent for silicone curable compositions, and is a main component which improves the adhesiveness of a silicone resin and a base material. It is thought that the segment of Formula (3) which exists in (E) is effective for base material adhesion|attachment, and it is estimated that an aromatic ring is functioning especially. When the base material is plastic, it is considered that the aromatic ring is also contained in the plastic, the π electrons of the aromatic ring act, and the adhesion is improved by the stacking effect. Moreover, the segment which has a Si-H group exists in the vicinity of an aromatic ring segment, and it is thought that the bond formation by Si-H group and the functional group on the surface of a base material also contributed to adhesiveness improvement.

(E) As a compounding quantity of a component, it is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A)-(C)component, 0.05-5 mass parts is more preferable, 0.1-3 mass parts is still more preferable, 0.1-1 mass part A mass part is especially preferable. When a compounding quantity is less than 0.01 mass part, sufficient adhesion improvement effect is not acquired but on the other hand, when it exceeds 10 mass parts, the Si-H group in a silicone adhesive composition increases, and migration of the adhesive to a to-be-adhered body may arise.

The component (E) can be obtained by, for example, hydrosilylation addition of an organic compound (E1) represented by the following formula (5) and a compound (E2) having at least two Si-H groups in one molecule in the presence of a catalyst. .

(Wherein, R ¹⁴ to R ²¹ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and W is a divalent organic group selected from the following formula (6). and Z is independently a hydrocarbon group having 1 to 6 carbon atoms, and may have an ether group in the structure.

(Wherein, R ²² to R ²³ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and h is an integer of 1 or more.)

In Formula (5), R ¹⁴ to R ²¹ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine and bromine, and examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Especially, a hydrogen atom and a C1-C6 hydrocarbon group are preferable, and a hydrogen atom and a methyl group are more preferable.

W is a divalent organic group selected from Formula (6), and R ²² to R ²³ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine and bromine, and examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. In these, a hydrogen atom and a C1-C6 hydrocarbon group are preferable, and a hydrogen atom and a methyl group are more preferable. m is an integer of 1 or more, 1-8 are preferable and 1-5 are more preferable. When m is larger than 8, the adhesiveness with a base material may worsen because the alkyl group which occupies in a repeating unit increases.

Z is independently a C1-C6 divalent hydrocarbon group, and may have an ether group in a structure. Examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include the following.

Moreover, the ether group may be included in a molecule|numerator, and the following are mentioned.

(E1) Although what is shown below as a thing showing the specific structure of a component, etc. are mentioned, It is not limited to these. In addition, Me in a following formula represents a methyl group, respectively.

(E2) is a compound having at least two Si-H groups in one molecule, and is represented by the following average compositional formula (9).

R ²⁹ _v H _w SiO _(4-vw)/2 (9)

(Wherein, R ²⁹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, v>0, w>0, and 0<v+w≤3.)

Specific examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for R ²⁹ include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an allyl group, a hexenyl group, an alkenyl group, such as an octenyl group, and an aryl group, such as a phenyl group, etc. are mentioned. In addition, a part or all of the hydrogen atoms couple|bonded with the carbon atom of these groups may be substituted by the halogen atom or another group, A trifluoromethyl group, 3,3, 3- trifluoropropyl group, etc. are illustrated as a substituent. As R ^{29, a} saturated aliphatic group or aromatic group is preferable, and a methyl group and a phenyl group are more preferable.

(E2) Although what is shown below as a thing showing the specific structure of a component, etc. are mentioned, It is not limited to these. In addition, Me in a following formula represents a methyl group, respectively.

(E) is a compound obtained by hydrosilylation addition of (E1) and (E2), which adds the alkenyl group which (E1) has and the Si-H group which (E2) has. At this time, all Si-H groups of (E2) are not reacted, and at least one must be left. This is in order to remain|survive the functional group for adding to the said composition when adding and using the compound of this invention to a silicone curable composition, By adding, the function of the compound of this invention is provided to a composition.

With respect to the alkenyl group of (E1) and the Si-H group of (E2), if the respective mole numbers are me1 and me2, the molar ratio at the time of the reaction is 1<(me2)/(me1)<14, preferably It is 1<(me2)/(me1)<10, More preferably, it is 1<(me2)/(me1)<8. When (me2)/(me1) is less than 1, the Si-H group necessary for addition does not remain, and when (ma2)/(ma1) is greater than 14, the repeating unit derived from (a1) in (A1) is There are cases in which a sufficient function cannot be exhibited due to the decrease.

In order to cure the alkenyl group of (E1) and the Si-H group of (E2) by hydrosilylation addition, a platinum group metal-based catalyst is required. Examples of the central metal include platinum, palladium, iridium, rhodium, osmium, and ruthenium. Among them, platinum is suitable. Examples of the platinum catalyst include chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and a reaction product of chloroplatinic acid and vinyl group-containing siloxane.

The amount of the platinum group catalyst is preferably such that the amount of metal is 0.1 to 200 ppm with respect to the total amount of (E1) and (E2), and more preferably 0.3 to 180 ppm. When the amount is 0.1 ppm or less, the reaction is slow and may not proceed sufficiently, and when it is 200 ppm or more, the catalyst removal after completion of the reaction becomes insufficient, so that the catalyst remains in the compound and storage stability may deteriorate.

Preparation (E) by hydrosilylation addition of the alkenyl group of (E1) and the Si-H group of (E2) is performed by a conventional method. That is, it is produced by introducing (E1) having an alkenyl group and a platinum group catalyst into a reaction vessel, adding (E2) having a Si-H group, and mixing with heat. After completion of the reaction, impurities are removed and purified by distillation under reduced pressure. In the production, a solvent may be optionally used, and specifically, aromatic hydrocarbon solvents such as toluene and xylene, hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, iso Aliphatic hydrocarbon solvents such as paraffin, hydrocarbon solvents such as industrial gasoline, petroleum benzine and solvent naphtha, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- Ketone solvents, such as heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, cyclohexanone, etc. can be used.

[(F) component]

Silicon compound containing 0.15 moles or more of alkenyl groups in 100 g

(F) A component is a component for suppressing the raise of the adhesive force with respect to a to-be-adhered body with time. When the adhesion enhancer of (E) is used, adhesion to the substrate is improved, and at the same time, when the silicone curable composition is used as an adhesive for an adhesive article, the adhesion to the adherend increases with time. F) is valid. For this reason, by adding a small amount of an additive with a large amount of vinyl groups to the base material with a small amount of vinyl groups in the silicone adhesive, the crosslinking density of the entire adhesive layer increases, thereby increasing the hardness of the adhesive layer, making it difficult to penetrate the adherend. It is presumed that there is

(F) The quantity of the alkenyl group contained in component is 0.15 mol or more per 100 g of organopolysiloxane, Preferably it is 0.18 mol or more, More preferably, it is 0.20 mol or more. When it is less than 0.15 mol, the inhibitory effect of an adhesive force increase may become weak. Although the upper limit is not specifically limited, It can be set as 2.0 mol or less. Moreover, it is preferable to have at least 1 siloxane bond in 1 molecule.

As an alkenyl group, a C2-C10 thing is preferable, For example, alkenyl groups, such as a vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, etc. cycloalkenylalkyl groups such as acryloylalkyl group, methacryloylalkyl group, and cyclohexenylethyl group, and alkenyloxyalkyl groups such as vinyloxypropyl group. Among them, a vinyl group is preferable.

(F) The range of 0.1-20,000 mPa*s is preferable, and, as for the viscosity (25 degreeC) of component, the range of 1-10,000 mPa*s is more preferable. In addition, a viscosity is the value measured with the rotational viscometer.

(F) The silicon compound represented by the following average compositional formula (10) as an example of a component, and 0.15 mol or more of alkenyl groups are contained in 100 g is mentioned. In the formula, n is 0.1 to 100, p is 0.1 to 100, and q is 0.01 to 10.

(F) Although the thing shown below is mentioned further as a specific example of a component, It is not limited to these. In addition, Me and Vi in a following formula represent a methyl group and a vinyl group, respectively.

(F) As a compounding quantity of a component, it is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A)-(C)component, 0.05-5 mass parts is preferable, and 0.1-3 mass parts is more preferable. When it is less than 0.01 mass part, the adhesive force increase inhibitory effect mentioned above will become weak, and when more than 10 mass parts, sclerosis|hardenability may worsen because a crosslinking point increases too much.

[(G) component]

Component (G) is a control agent, and the control agent is added in order to prevent the treatment liquid from thickening or gelling due to initiation of an addition reaction before heat curing when the silicone pressure-sensitive adhesive composition is combined or coated on a substrate. The reaction controlling agent coordinates with the platinum group metal serving as the addition reaction catalyst to suppress the addition reaction, and when heat-cured, the coordination is released and catalytic activity is expressed. Any reaction controlling agent conventionally used for the addition reaction curable silicone composition can be used. Specific examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, ethynylcyclohexanol (1-e thynyl-1-cyclohexanol), 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethyl Siloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butynoxy)dimethylsilane, 1,3,5,7- tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, maleic acid ester, adipic acid ester, etc. can

(G) 0.01-5 mass parts is preferable with respect to 100 mass parts of total amounts of (A)-(C)component, and, as for the compounding quantity of a control agent, 0.05-2 mass parts is more preferable.

[(H) component]

Component (H) is a component for making pendants of siloxane in the cross-linked network of the composition by adding it to the silicone pressure-sensitive adhesive composition, and the presence of pendants of siloxane plays a role in inhibiting the increase in adhesion to an adherend with time. can do. When the silicone curable composition is used as an adhesive for an adhesive article, the adhesion to the adherend increases with time, but by using component (H), adhesion to the substrate is improved and the increase in the adhesion to the adherend can be suppressed. have.

Specifically, (H) an organohydrogenpolysiloxane represented by the following average composition formula (7) (however, excluding the component (C)) can be added.

(Wherein, R ²⁴ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms. i is an integer of 1 or more, j is an integer of 1 or more, k is an integer of 1 or more, l and m are integers of 0 or more, and 5 ≤i+j+k+l+m≤500.)

In the formula (7), R ²⁴ is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, or a vinyl group alkenyl groups, such as group, allyl group, hexenyl group, and octenyl group, and aryl groups, such as a phenyl group, etc. are mentioned. In addition, a part or all of the hydrogen atoms couple|bonded with the carbon atom of these groups may be substituted by the halogen atom or another group, A trifluoromethyl group, 3,3, 3- trifluoropropyl group, etc. are illustrated as a substituent. Among these, a saturated aliphatic group or an aromatic group is preferable, and a methyl group and a phenyl group are more preferable.

i is an integer of 1 or more, 1-3 are preferable and i=1 is more preferable. The organohydrogenpolysiloxane having a Si-H group only at the molecular terminal is preferable, and the organohydrogenpolysiloxane having one Si-H group at the molecular terminal is more preferable. (F) As for the component, the thing of the structure which has Si-H group which bridge|crosslinking arises at the terminal of polysiloxane from the point similar to the above is effective, and polysiloxane which has one Si-H group in 1 molecule is especially suitable. j is an integer of 1 or more, k is an integer of 1 or more, l and m are integers of 0 or more, 5≤i+j+k+l+m≤500, preferably 7≤i+j+k+l+m ≤300, more preferably 8≤i+j+k+1+m≤200. When i+j+k+l+m is less than 5, the effect of the pendant as described above is not sufficiently exhibited, and when i+j+k+l+m is greater than 500, the pendant portion is too long When molecules entangle with each other, suppression of an increase in adhesive force may become insufficient.

(H) Although what is shown below as a thing showing the specific structure of a component, etc. are mentioned, It is not limited to these. In addition, i-Pr and n-Bu in a following formula represent an isopropyl group and a normal butyl group, respectively. Q is 4-300, 4-100 are preferable, and R is 1-10.

(H) The compounding quantity of component is 0.01-100 mass parts with respect to 100 mass parts of total amounts of said (A)-(C)component, 0.05-50 mass parts is preferable, 0.1-20 mass parts is more preferable, 0.5-10 mass parts A mass part is more preferable. When the compounding amount is less than 0.01 parts by mass, the above-described effect of suppressing the increase in adhesive force is weakened, and when the amount is more than 100 parts by mass, the Si-H groups in the silicone pressure-sensitive adhesive composition increase, whereby the pressure-sensitive adhesive migration to the adherend may occur.

[etc]

(solvent)

When all the above-mentioned components are mixed, since a viscosity may become high and handling may become difficult, in order to dilute, you may add a solvent arbitrarily. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane and isoparaffin, industrial gasoline, Hydrocarbon solvents such as petroleum benzine and solvent naphtha, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl Ketone solvents such as ketone, acetonylacetone, and cyclohexanone, ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate, diethyl ether, dipropyl ether, diisopropyl Ether solvents such as ether, dibutyl ether, 1,2-dimethoxyethane, 1,4-dioxane, 2-methoxyethyl acetato, 2-ethoxyethyl acetato, propylene glycol mono Solvents having ester and ether moieties, such as methyl ether acetato and 2-butoxyethyl acetato, hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris Siloxane solvents, such as (trimethylsiloxy)methylsilane and tetrakis(trimethylsiloxy)silane, or these mixed solvents, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

[Adhesive article]

By coating and curing the silicone composition on at least one side of the substrate, it is possible to obtain an adhesive article having a substrate and an adhesive layer formed on at least one side of the substrate.

As the base material to which the silicone pressure-sensitive adhesive is applied, a plastic film made of paper or plastic, glass, and metal are selected. Examples of the paper include fine paper, coated paper, art paper, glassine paper, polyethylene laminate paper, kraft paper, and the like. Examples of plastic films include polyethylene film, polypropylene film, polyester film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polytetrafluoroethylene film, polystyrene film, ethylene- A vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a triacetyl cellulose film, a polyether ether ketone film, a polyphenylene sulfide film, etc. are mentioned. There is no restriction|limiting in particular with respect to thickness, a kind, etc. also about glass, The thing which carried out chemical strengthening process etc. may be sufficient. Moreover, glass fiber can also be applied, and glass fiber may use what was combined with other resin as a single-piece|unit. Examples of the metal include aluminum foil, copper foil, gold foil, silver foil and nickel foil.

Among these substrates, the silicone pressure-sensitive adhesive of the present invention is preferably used with a plastic film as the substrate. BACKGROUND ART An adhesive tape or adhesive sheet produced using various plastic films as a base material is used for various purposes. Glass, metal, plastic, etc. are mentioned as a to-be-adhered body. As an adhesive article, it is used for the protective film of various displays, an electrical insulation tape, a masking tape, a splicing tape, pasting to skin, etc. Examples of displays include television sets, computer monitors, portable information terminal monitors, monitoring monitors, video cameras, digital cameras, mobile phones, portable information terminals, instrument panel displays for automobiles, and instrument panel displays for various facilities, devices and equipment; Various touch panels, flat panel displays (FPD), etc. for displaying characters, symbols, such as a liquid crystal display, an organic electroluminescent display, an automatic vending machine, and an automatic teller machine, and an image are mentioned.

Although the thickness of a base material, especially a base film is not limited, 1-200 micrometers is preferable, and 5-150 micrometers is more preferable. In the case of a base film, the adhesive film provided with the base film and the adhesive layer formed by coating and hardening the said silicone composition on at least single side|surface of a base film is obtained.

In order to improve the adhesiveness of a base material and an adhesive layer, you may use what was subjected to a primer treatment, corona treatment, etching treatment, plasma treatment, or sandblasting treatment. Preferably, corona treatment is good. A primer treatment may not be necessary and it can be set as the structure without a primer layer.

It is preferable that the surface of the substrate opposite to the pressure-sensitive adhesive layer is subjected to a surface treatment such as wound prevention, contamination prevention, fingerprint adhesion prevention, anti-glare, anti-reflection, antistatic or the like treatment. After coating an adhesion layer on a base material, each said surface treatment may be carried out, and after surface-treating, you may apply an adhesion layer.

As a wound prevention process (hard-coat process), the process by hard-coat agents, such as an acrylate type, a silicone type, an oxetane type, an inorganic type, and an organic-inorganic hybrid type, is mentioned.

Examples of the antifouling treatment include treatment with an antifouling agent such as a fluorine-based, silicon-based, ceramic-based, or photocatalyst-based treatment.

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

The coating method may be applied using a known coating method, for example, comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, immersion coating, Cast coating etc. are mentioned.

Although there is no restriction|limiting in particular about the coating amount, As thickness of the adhesive layer after hardening, it can be set as 0.1-300 micrometers, Preferably it is 0.5-200 micrometers.

In general, most of the catalysts are not mixed in the silicone adhesive. The catalyst is uniformly mixed before use. The curing conditions may be 20 seconds to 10 minutes at 80 to 150°C, but the curing conditions are not limited thereto.

The range of 0.01-12.0N/25mm is preferable, as for the adhesive force of the silicone adhesive composition after hardening, 0.01-10.0N/25mm is more preferable, 0.01-8.0N/25mm is still more preferable. Rework becomes easier by affixing with a to-be-adhered body at 0.01 N/25 mm or more, and setting it as 12.0 N/25 mm or less.

Example

Hereinafter, the present invention will be specifically described with reference to Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, Me represents a methyl group, Vi represents a vinyl group, and n-Bu represents a normal butyl group.

[Production Example 1: (E) component]

1,3,5,7-tetramethylcyclotetrasiloxane 144.3 g (0.6 mol), toluene 144.3 g, 1,3-die in a 500 mL separable flask equipped with a stirrer, thermometer, dropping funnel and reflux cooling tube. 0.03 g of toluene solution containing 0.5 mass % of platinum powder of vinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex was introduce|transduced, mixed and stirred, and it heated to about 60-65 degreeC. 61.7 g (0.2 mol) of 2,2-bis(4-allyloxyphenyl)propane was dripped there from the dropping funnel, after completion|finish of dripping, it heated to about 80-85 degreeC, and made it react at this temperature for 1 hour. After completion of the reaction, 0.3 g of activated carbon was added and mixed for 2 hours in order to remove platinum as a catalyst, and then the activated carbon was removed by filtration. The obtained liquid was concentrated under reduced pressure at 90°C for 8 hours to obtain a colorless and transparent liquid. It turned out that it was a mixture of the compounds shown below when investigated, and the compound of z1=2 with z1=0-4 was a main component.

[Production Example 2]

1,3,5,7-tetramethylcyclotetrasiloxane 96.2 g (0.4 mol), toluene 96.2 g, 1,3-die in a 500 mL separable flask equipped with a stirrer, thermometer, dropping funnel and reflux cooling tube. 0.03 g of toluene solution containing 0.5 mass % of platinum powder of a vinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex was introduce|transduced, mixed and stirred, and it heated to about 60-65 degreeC. 61.7 g (0.2 mol) of 2,2-bis(4-allyloxyphenyl)propane was added dropwise thereto from a dropping funnel, and after completion of the dropping, the mixture was heated to about 80 to 85°C, and reacted at this temperature for 2 hours. After completion of the reaction, 0.3 g of activated carbon was added and mixed for 2 hours in order to remove platinum as a catalyst, and then the activated carbon was removed by filtration. The obtained liquid was concentrated under reduced pressure at 90°C for 8 hours to obtain a colorless and transparent liquid. As a result of the investigation, it was found that it was a mixture of the compounds shown in Preparation Example 1, and the compound of z1=3 with z1=0-4 was the main component.

[Comparative Preparation Example 1]

In a 500 mL separable flask equipped with a stirring device, thermometer, dropping funnel, and reflux cooling tube, 86.54 g (0.7 mol) of dimethyldimethoxysilane and 52.89 g (0.4 mol) of methylvinyldimethoxysilane, and methanol 8.00 g is introduced, KOH and 100 g of distilled water in an amount of 50 ppm in total of the two types of silanes are added dropwise from a dropping funnel, reacted for 2 hours under methanol reflux, and then concentrated under reduced pressure at 60° C. for 4 hours. Siloxane containing vinyl groups blocked with silanol or methoxy groups was obtained. The compound was obtained by mixing and stirring the obtained oil and 3-glycidoxypropyl trimethoxysilane at room temperature for about 1 hour so that it might become 50/50 by mass ratio.

<Silicone pressure-sensitive adhesive composition>

[Example 1]

(A) 90 parts by mass of polydimethylsiloxane having a vinyl group represented by the following average composition formula (a);

_{(B) Me 3 SiO 1/} 2 units and SiO containing ₂ units, and (Me ₃ SiO _1/2 units) / (SiO ₂₎ of the molar ratio is 0.85 organo 60% by weight of the polysiloxane in toluene solution to light 10 parts by mass as a volatile matter;

(C) 0.29 parts by mass of organohydrogenpolysiloxane represented by the following average compositional formula (c-1);

(C) 0.41 parts by mass of organohydrogenpolysiloxane represented by the average composition formula (c-2), and

(G) 0.16 mass parts of ethynylcyclohexanol was mixed, it diluted with toluene, and the mixture of 60 mass % of active ingredients was obtained.

50 parts by mass of toluene is added to 100 parts by mass of a mixture of 60% by mass of the obtained active ingredient, (D) Platinum powder 0.5 of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex 0.5 parts by mass of a toluene solution containing mass%, 2 parts by mass of the compound obtained in Production Example 1 as (E) component, which is the adhesion improving component of the present invention, and the following average compositional formula (f-1) as (F) component The silicone pressure-sensitive adhesive composition was produced by adding 2 parts by mass of a silicon compound having a viscosity of 24.0 mPa·s at 25°C and a vinyl group content of 0.53 mol in 100 g.

[Example 2]

0.5 parts by mass of the compound obtained in Production Example 1, and 0.5 parts by mass of the silicon compound represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s and having a vinyl group content of 0.53 moles contained in 100 g of 0.5 parts by mass It carried out similarly to 1, and produced the silicone adhesive composition.

[Example 3]

0.4 parts by mass of the compound obtained in Production Example 1, represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s, and 0.4 parts by mass of a silicon compound having a vinyl group content of 0.53 mol contained in 100 g of Examples It carried out similarly to 1, and produced the silicone adhesive composition.

[Reference example]

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 3, except that the silicon compound represented by the average compositional formula (f-1) and having a viscosity of 24.0 mPa·s and a vinyl group content of 0.53 mol contained in 100 g was not added.

[Example 4]

0.3 parts by mass of the compound obtained in Production Example 1, which is represented by the average compositional formula (f-1), has a viscosity of 24.0 mPa·s, and is 0.3 parts by mass of a silicon compound having a vinyl group content of 0.53 mol contained in 100 g, except that 0.3 parts by mass It carried out similarly to 1, and produced the silicone adhesive composition.

[Example 5]

0.2 parts by mass of the compound obtained in Production Example 1, represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s and 0.2 mass parts of a silicon compound having a vinyl group content of 0.53 moles contained in 100 g of 0.2 parts by mass It carried out similarly to 1, and produced the silicone adhesive composition.

[Example 6]

0.12 parts by mass of the organohydrogenpolysiloxane represented by the average composition formula (c-1), 0.16 parts by mass of the organohydrogenpolysiloxane represented by the average composition formula (c-2), and 0.4 parts by mass of the compound obtained in Production Example 1 The silicone pressure-sensitive adhesive composition was carried out in the same manner as in Example 1, except that the silicon compound represented by the part, average composition formula (f-1), having a viscosity at 25°C of 24.0 mPa·s, and having a vinyl group content of 0.53 mol in 100 g was 0.4 parts by mass. has produced

[Example 7]

0.46 parts by mass of the organohydrogenpolysiloxane represented by the average composition formula (c-1), 0.66 parts by mass of the organohydrogenpolysiloxane represented by the average composition formula (c-2), and 0.4 parts by mass of the compound obtained in Production Example 1 The silicone pressure-sensitive adhesive composition was carried out in the same manner as in Example 1, except that the silicon compound represented by the part, average composition formula (f-1), having a viscosity at 25°C of 24.0 mPa·s, and having a vinyl group content of 0.53 mol in 100 g was 0.4 parts by mass. has produced

[Example 8]

0.4 parts by mass of the compound obtained in Preparation Example 1, represented by the average composition formula (f-1), the compound obtained in Preparation Example 2 is a silicon compound having a viscosity of 24.0 mPa·s at 25°C, and a vinyl group content of 0.53 moles in 100 g Except having made into 0.4 mass part, it carried out similarly to Example 1, and produced the silicone adhesive composition.

[Example 9]

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 3, except that the silicon compound represented by the average compositional formula (f-1) and having a viscosity at 25°C of 24.0 mPa·s and having a vinyl group content of 0.53 moles contained in 100 g was 0.2 parts by mass. did.

[Example 10]

A silicone pressure-sensitive adhesive composition was prepared in the same manner as in Example 3, except that 0.8 parts by mass of a silicon compound represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s at 25°C, and having a vinyl group content of 0.53 moles contained in 100 g was 0.8 parts by mass. did.

[Example 11]

Instead of using 0.4 parts by mass of a silicon compound represented by the average compositional formula (f-1), having a viscosity at 25°C of 24.0 mPa·s and having a vinyl group content of 0.53 mol in 100 g, represented by the following formula (f-2) It carried out similarly to Example 3, and produced the silicone adhesive composition except using 0.2 mass parts of silicon compounds whose vinyl group amount contained in 100 g is 0.86 mol.

[Example 12]

It is represented by a formula (f-2), and except having made the silicon compound whose vinyl group amount 0.86 mol contained in 100 g into 0.4 mass part, it carried out similarly to Example 11, and produced the silicone adhesive composition.

[Example 13]

Instead of using 0.4 parts by mass of a silicon compound represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s and having a vinyl group content of 0.53 moles contained in 100 g, 0.4 parts by mass, represented by the following formula (f-3), 100 g The silicone pressure-sensitive adhesive composition was produced in the same manner as in Example 3 except that 0.4 parts by mass of the silicon compound having a vinyl group amount of 0.20 mol contained therein was used.

[Example 14]

A silicone pressure-sensitive adhesive composition was produced in the same manner as in Example 13, except that it is represented by the average compositional formula (f-3) and the amount of vinyl groups contained in 100 g is 0.8 parts by mass of the silicon compound having 0.20 mol.

[Example 15]

(A) 100 parts by mass of polydimethylsiloxane having a vinyl group represented by the following average composition formula (a);

(C) 0.32 parts by mass of organohydrogenpolysiloxane represented by the following average compositional formula (c-1);

(C) 0.46 parts by mass of organohydrogenpolysiloxane represented by the average compositional formula (c-2), and

(G) 0.18 mass parts of ethynylcyclohexanol was mixed, it diluted with toluene, and the mixture of 60 mass % of active ingredients was obtained.

50 mass parts of toluene is added to 100 mass parts of obtained mixture, (D) Toluene containing 0.5 mass % of platinum powder of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex. 0.5 parts by mass of the solution, 0.4 parts by mass of the adhesion enhancer described in Production Example 1 as component (E) as the adhesion enhancing component, and the average compositional formula (f-1), and the viscosity at 25° C. is 24.0 mPa s, and in 100 g A silicone pressure-sensitive adhesive composition was prepared by adding 0.4 parts by mass of a silicon compound having an amount of contained vinyl groups of 0.53 mol.

[Example 16]

(A) 80 parts by mass of polydimethylsiloxane having a vinyl group represented by the following average composition formula (a);

_{(B) Me 3 SiO 1/} 2 units and SiO containing ₂ units, and (Me ₃ SiO _1/2 units) / (SiO ₂₎ of the molar ratio is 0.85 organo 60% by weight of the polysiloxane in toluene solution to light 20 parts by mass as a volatile matter;

(C) 0.26 parts by mass of organohydrogenpolysiloxane represented by the following average compositional formula (c-1);

(C) 0.36 parts by mass of organohydrogenpolysiloxane represented by the average compositional formula (c-2), and

(G) 0.18 mass parts of ethynylcyclohexanol was mixed, it diluted with toluene, and the mixture of 60 mass % of active ingredients was obtained.

50 mass parts of toluene is added to 100 mass parts of obtained mixture, (D) Toluene containing 0.5 mass % of platinum powder of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex. 0.5 parts by mass of the solution, 0.4 parts by mass of the adhesion improving agent described in Production Example 1 as component (E) as the adhesion enhancing component of the present invention, and represented by the average compositional formula (f-1), the viscosity is 24.0 mPa s and in 100 g A silicone pressure-sensitive adhesive composition was prepared by adding 0.4 parts by mass of a silicon compound having an amount of contained vinyl groups of 0.53 mol.

[Example 17]

(A) 60 parts by mass of polydimethylsiloxane having a vinyl group represented by the following average composition formula (a);

_{(B) Me 3 SiO 1/} 2 units and SiO containing ₂ units, and (Me ₃ SiO _1/2 units) / (SiO ₂₎ of the molar ratio is 0.85 organo 60% by weight of the polysiloxane in toluene solution to light 40 parts by mass as volatile matter;

(C) 0.19 parts by mass of organohydrogenpolysiloxane represented by the following average compositional formula (b);

(C) 0.27 parts by mass of organohydrogenpolysiloxane represented by the average compositional formula (c-2), and

(G) 0.18 mass parts of ethynylcyclohexanol was mixed, it diluted with toluene, and the mixture of 60 mass % of active ingredients was obtained.

50 mass parts of toluene is added to 100 mass parts of obtained mixture, (D) Toluene containing 0.5 mass % of platinum powder of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex. 0.5 parts by mass of the solution, 0.4 parts by mass of the adhesion enhancer described in Production Example 1 as component (E) as the adhesion enhancing component, and the average compositional formula (f-1), and the viscosity at 25° C. is 24.0 mPa s, and in 100 g A silicone pressure-sensitive adhesive composition was prepared by adding 0.4 parts by mass of a silicon compound having an amount of contained vinyl groups of 0.53 mol.

[Example 18]

0.4 mass parts of organohydrogenpolysiloxane represented by the following average composition formula (h-1) as (H) component further to the silicone adhesive composition produced in Example 3 was added, and the silicone adhesive composition was produced.

[Example 19]

To the silicone adhesive composition produced in Example 3, 0.4 mass parts of organohydrogenpolysiloxane represented by the following average composition formula (h-2) as (H)component was further added to the silicone adhesive composition, and the silicone adhesive composition was produced.

[Example 20]

To the silicone adhesive composition produced in Example 3, 0.4 mass parts of organohydrogenpolysiloxane represented by the following average composition formula (h-3) as (H)component was further added to the silicone adhesive composition, and the silicone adhesive composition was produced.

[Example 21]

To the silicone adhesive composition produced in Example 3, 0.4 mass parts of organohydrogenpolysiloxane represented by the following average composition formula (h-4) as (H) component was further added to the silicone adhesive composition, and the silicone adhesive composition was produced.

[Example 22]

Except having added 0.8 mass parts of organohydrogenpolysiloxane represented by the average composition formula (h-2), it carried out similarly to Example 19, and produced the silicone adhesive composition used for a test.

[Comparative Example 1]

Examples except that the compound obtained in Preparation Example 1 was not added, and the silicon compound represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s and having a vinyl group content of 0.53 mol in 100 g, was not added. It carried out similarly to 1, and produced the silicone adhesive composition.

[Comparative Example 2]

2,2-bis(4-allyl) instead of the compound obtained in Production Example 1 and the silicon compound represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s and having a vinyl group content of 0.53 mol in 100 g Except having used 0.4 mass part of oxyphenyl) propane, it carried out similarly to Example 1, and produced the silicone adhesive composition.

[Comparative Example 3]

The silicone pressure-sensitive adhesive composition used in the test was prepared in the same manner as in Comparative Example 2, except that 0.4 parts by mass of a silicon compound represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s and having a vinyl group content of 0.53 mol in 100 g, was added. made

[Comparative Example 4]

The compound obtained by Preparation Example 1 and the compound obtained by Comparative Preparation Example 1 instead of the silicon compound represented by the average compositional formula (f-1), having a viscosity of 24.0 mPa·s and having a vinyl group content of 0.53 moles contained in 100 g, Except using, it carried out similarly to Example 1, and produced the silicone adhesive composition.

About the above-mentioned silicone adhesive composition, the following method evaluated adhesiveness and adhesive force.

<Adhesiveness>

With respect to 100 parts by mass of a mixture of 60 mass % of the active ingredient, (D) a curing catalyst and the components (E) and (F) described above were added to prepare a treatment bath in which the mixture was stirred quickly, and this was 23 μm thick, Using an applicator, it set and coated so that the thickness of the adhesive layer after hardening might be set to 30 micrometers on a 25 mm-width polyethylene terephthalate (PET) film. After air-drying this for 1 minute with a dryer at 130°C, and allowing the produced adhesive article to stand still under certain conditions, scrape the adhesive layer with a protrusion such as a nail or cutter, and rub this part with the convex part of the finger. evaluated together. In addition, the conditions under which the adhesive article was left still were 4 conditions: 1 day at room temperature, 1 day at 60 degreeC/90%RH, 1 day at 85 degreeC/85%RH, and 7 days at 60 degreeC/90%RH. A result is shown based on the following reference|standard.

(standard)

○: The adhesive layer does not peel from the substrate

x: the adhesive layer peels from the base material

<Adhesiveness>

With respect to 100 parts by mass of a mixture containing 60% by mass of the active ingredient, a curing catalyst and components (E) and (F) described above were added to prepare a treatment bath that was rapidly mixed and stirred, and this was made of polyethylene having a thickness of 23 μm and a width of 25 mm. After coating using an applicator so that the thickness after hardening might be set to 30 micrometers to a terephthalate (PET) film, it heated and hardened under the conditions of 130 degreeC/1 minute, and the adhesive tape was produced. This adhesive tape was affixed to a glass plate, and it crimped|bonded by making two reciprocating rollers coated with the rubber layer of weight 2 kg. The glass plate to which the adhesive tape is bonded is placed in a constant temperature bath to which a constant humidity and temperature is applied for a predetermined number of days, and then taken out, and the force required to peel the tape off the glass plate at an angle of 180° at a speed of 300 mm/min using a tensile tester (N/ 25 mm).

adhesion
Yes
(E) component
(F) component
(H) component 1 day at room temperature at 60℃/90%RH
1 day At 85℃/85%RH
1 day at 60℃/90%RH
7 days Example 1 Preparation Example 1 (f-1)
2.0 parts by mass does not exist ○ ○ ○ ○ Example 2 Preparation Example 1 (f-1)
0.5 parts by mass does not exist ○ ○ ○ ○ Example 3 Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Reference example Preparation Example 1 does not exist does not exist ○ ○ ○ ○ Example 4 Preparation Example 1 (f-1)
0.3 parts by mass does not exist ○ ○ ○ ○ Example 5 Preparation Example 1 (f-1)
0.2 parts by mass does not exist ○ ○ ○ ○ Example 6 Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Example 7 Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Example 8 Preparation 2 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Example 9 Preparation Example 1 (f-1)
0.2 parts by mass does not exist ○ ○ ○ ○ Example 10 Preparation Example 1 (f-1)
0.8 parts by mass does not exist ○ ○ ○ ○ Example 11 Preparation Example 1 (f-1)
0.2 parts by mass does not exist ○ ○ ○ ○ Example 12 Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Example 13 Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Example 14 Preparation Example 1 (f-1)
0.8 parts by mass does not exist ○ ○ ○ ○ Example 15 Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Example 16 Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Example 17 Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ ○ ○ ○ Example 18 Preparation Example 1 (f-1)
0.4 parts by mass (h-1)
0.4 parts by mass ○ ○ ○ ○ Example 19 Preparation Example 1 (f-1)
0.4 parts by mass (h-2)
0.4 parts by mass ○ ○ ○ ○ Example 20 Preparation Example 1 (f-1)
0.4 parts by mass (h-3)
0.4 parts by mass ○ ○ ○ ○ Example 21 Preparation Example 1 (f-1)
0.4 parts by mass (h-4)
0.4 parts by mass ○ ○ ○ ○ Example 22 Preparation Example 1 (f-1)
0.4 parts by mass (h-2)
0.8 parts by mass ○ ○ ○ ○ Comparative Example 1 does not exist does not exist does not exist × × × × Comparative Example 2 Raw material of Preparation Example 1 does not exist does not exist ○ × × × Comparative Example 3 Raw material of Preparation Example 1 (f-1)
0.4 parts by mass does not exist ○ × × × Comparative Example 4 Comparative Preparation Example 1 does not exist does not exist ○ × × ×

Adhesion (N/25mm)
Yes
(E) component
(F) component
(H) component 1 day at room temperature at 60℃/90%RH
1 day At 85℃/85%RH
1 day at 60℃/90%RH
7 days Example 1 Preparation Example 1 (f-1)
2.0 parts by mass does not exist 0.10 1.11 1.08 1.85 Example 2 Preparation Example 1 (f-1)
0.5 parts by mass does not exist 0.06 0.23 0.29 1.32 Example 3 Preparation Example 1 (f-1)
0.4 parts by mass does not exist 0.06 0.21 0.34 0.36 Reference example Preparation Example 1 does not exist does not exist 0.20 1.06 1.52 1.55 Example 4 Preparation Example 1 (f-1)
0.3 parts by mass does not exist 0.07 0.27 0.30 0.30 Example 5 Preparation Example 1 (f-1)
0.2 parts by mass does not exist 0.06 0.20 0.26 0.24 Example 6 Preparation Example 1 (f-1)
0.4 parts by mass does not exist 0.08 0.48 0.77 0.95 Example 7 Preparation Example 1 (f-1)
0.4 parts by mass does not exist 0.07 0.36 0.55 0.50 Example 8 Preparation 2 (f-1)
0.4 parts by mass does not exist 0.07 0.29 0.32 0.42 Example 9 Preparation Example 1 (f-1)
0.2 parts by mass does not exist 0.11 0.33 0.59 0.95 Example 10 Preparation Example 1 (f-1)
0.8 parts by mass does not exist 0.08 0.18 0.33 0.68 Example 11 Preparation Example 1 (f-1)
0.2 parts by mass does not exist 0.07 0.31 0.34 0.31 Example 12 Preparation Example 1 (f-1)
0.4 parts by mass does not exist 0.05 0.16 0.48 0.44 Example 13 Preparation Example 1 (f-1)
0.4 parts by mass does not exist 0.13 0.49 0.47 0.61 Example 14 Preparation Example 1 (f-1)
0.8 parts by mass does not exist 0.08 0.25 0.38 0.42

Adhesion (N/25mm)
(E) component
(F) component
(H) component 1 day at room temperature at 60℃/90%RH
1 day At 85℃/85%RH
1 day at 60℃/90%RH
7 days Example 15 Preparation Example 1 (f-1)
0.4 parts by mass does not exist 0.10 0.38 0.49 0.61 Example 16 Preparation Example 1 (f-1)
0.4 parts by mass does not exist 0.12 0.70 0.85 1.21 Example 17 Preparation Example 1 (f-1)
0.4 parts by mass does not exist 2.14 5.06 4.71 5.30 Example 18 Preparation Example 1 (f-1)
0.4 parts by mass (h-1)
0.4 parts by mass 0.06 0.13 0.23 0.35 Example 19 Preparation Example 1 (f-1)
0.4 parts by mass (h-2)
0.4 parts by mass 0.06 0.14 0.20 0.20 Example 20 Preparation Example 1 (f-1)
0.4 parts by mass (h-3)
0.4 parts by mass 0.04 0.16 0.25 0.36 Example 21 Preparation Example 1 (f-1)
0.4 parts by mass (h-4)
0.4 parts by mass 0.04 0.22 0.30 0.44 Example 22 Preparation Example 1 (f-1)
0.4 parts by mass (h-2)
0.8 parts by mass 0.06 0.16 0.14 0.34 Comparative Example 1 does not exist does not exist does not exist 0.05 0.07 0.22 0.14 Comparative Example 2 Raw material of Preparation Example 1 does not exist does not exist 0.10 with glass
implementation with glass
implementation with glass
implementation Comparative Example 3 Raw material of Preparation Example 1 (f-1)
0.4 parts by mass does not exist 0.04 0.20 with glass
implementation with glass
implementation Comparative Example 4 Comparative Preparation Example 1 does not exist does not exist 0.03 0.04 0.12 0.07

In Examples 1-22, the adhesiveness improvement with a base material was possible with one coating, and the base material adhesiveness in said 4 conditions was all favorable. It is thought that this is expressed by interaction at an interface by the stacking effect of the phenyl group of (E) component, and a base material and (pi) electron. Comparing Examples 2 to 14 and 18 to 22 with Reference Examples, it can be seen that the width of the increase in adhesive strength over time is increased in the Reference Example, which also interacts with the silanol group on the glass surface by having a phenyl group. I think this is because it works. However, by adding the component (F), it is possible to suppress the increase in the adhesive force with the passage of time, which increases the crosslinking density of the entire adhesive layer, thereby increasing the hardness of the adhesive layer, and it is difficult for the adhesive layer to be caught on the unevenness of the surface of the adherend. I think it is losing Moreover, also by using (H)component together, it turns out that the adhesive force rise with time is suppressed, maintaining base material adhesiveness.

On the other hand, in Comparative Example 1 in which no adhesion enhancer was added, adhesion could not be ensured. When the comparative manufacture example 1 was used, although adhesiveness could be ensured only in the initial stage, it was the result that the adhesiveness with the passage of time was inadequate. Moreover, also about the comparative examples 2 and 3 which used 2,2-bis (4-allyloxyphenyl) propane used as the raw material of (E) component, adhesiveness is inadequate also, as this factor, since the molecular weight is small only with a raw material, the mutual interaction with a base material is a factor. It was thought that the function was only partially functioning. As manufactured in Production Examples 1 and 2, it is thought that the effect is exhibited by using a thing having a large molecular weight to some extent. In the measurement of adhesive force, it was also suggested that an adhesive layer migrated to glass and hardening was inadequate.

Claims (7)

The silicone adhesive composition containing the following (A)-(F) component.
(A) organopolysiloxane represented by the following average composition formula (1), having at least two alkenyl group-containing organic groups in one molecule, and containing 0.0007 to 0.05 moles of alkenyl groups in 100 g: 40 to 100 parts by mass;

(Wherein, R ¹ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, and ^{at least two of R 1} includes an alkenyl group-containing organic group having 2 to 10 carbon atoms. a is an integer of 2 or more, b is An integer greater than or equal to 1, c is an integer greater than or equal to 0, d is an integer greater than or equal to 0, and 50≤a+b+c+d≤15,000.)
_{^{(B) R 2 3 SiO 1}} /2 units (wherein, R ² represents an alkenyl group of 1 to 10 carbon atoms in a monovalent hydrocarbon group or having 2 to 6 carbon atoms that does not have an aliphatic unsaturated bond independently.) And SiO _{4 / 2} contains the units and (R _{² 3} SiO _^1/2 units) / (SiO _4/2 units) molar ratio of the organo polysiloxane represented by 0.5 to 1.0 years of age: 0 to 60 parts by weight,
(However, the sum total of (A) and (B) component is 100 mass parts.)
(C) Organohydrogenpolysiloxane represented by the following average composition formula (2) and having at least three Si-H groups in one molecule: Si-H groups in molar ratio to the alkenyl groups of components (A) and (B) An amount that becomes 0.2 to 15 with
R ³ _e H _f SiO _(4-ef)/2 (2)
(Wherein, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e>0, f>0, and 0<e+f≤3.)
(D) (A), a platinum group metal catalyst for curing the alkenyl group of the component (B) and the Si-H group of (B) by hydrosilylation addition: the amount of metal with respect to the total amount of the components (A) to (C) 1 to 500 ppm as
(E) A compound having one or more repeating units represented by the following formula (3) and one or more Si-H groups in one molecule: 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of the components (A) to (C) mass part,

[Wherein, R ⁴ to R ¹¹ are the same or different kinds of hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and X is the following formula (4)

(Wherein, R ¹² to R ¹³ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and g is an integer of 1 or more.)
It is selected from the divalent organic group represented by, Y is independently a C1-C6 hydrocarbon group, and may have an ether group in the structure.]
(F) Silicon compound containing 0.15 mol or more alkenyl group in 100 g: 0.01-10 mass parts with respect to 100 mass parts of total amounts of said (A)-(C) component The silicone pressure-sensitive adhesive composition according to claim 1, further comprising 0.01 to 5 parts by mass of the (G) control agent with respect to 100 parts by mass of the total amount of the components (A) to (C). The method according to claim 1, wherein the component (E) is hydrosilylated by adding an organic compound (E1) represented by the following formula (5) and a compound (E2) having at least two Si-H groups in one molecule in the presence of a catalyst. It is a compound obtained, The silicone adhesive composition characterized by the above-mentioned.

(Wherein, R ¹⁴ to R ²¹ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and W is a divalent organic group selected from the following formula (6). and Z is independently a hydrocarbon group having 1 to 6 carbon atoms, and may have an ether group in the structure.

(Wherein, R ²² to R ²³ are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms, and h is an integer of 1 or more.) The silicone pressure-sensitive adhesive composition according to claim 1, wherein component (F) is a silicon compound having at least one siloxane bond in one molecule. The organohydrogenpolysiloxane according to claim 1, wherein (H) the organohydrogenpolysiloxane represented by the following average composition formula (7) (however, the component (C) is excluded)

(Wherein, R ²⁴ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms. i is an integer of 1 or more, j is an integer of 1 or more, k is an integer of 1 or more, l and m are integers of 0 or more, and 5 ≤i+j+k+l+m≤500.)
A silicone pressure-sensitive adhesive composition comprising 0.01 to 100 parts by mass based on the total amount of the components (A) to (C). An adhesive article comprising a substrate and an adhesive layer formed on at least one side of the substrate, wherein the adhesive layer is obtained by coating and curing the silicone pressure-sensitive adhesive composition according to any one of claims 1 to 5 on at least one side of the substrate sticky items. 7. The adhesive article according to claim 6, wherein the substrate is a plastic film.