TWI669365B - Silicone adhesive composition and adhesive article with excellent substrate adhesion - Google Patents

Abstract

It is an object of the present invention to provide a polysiloxane adhesive composition and an adhesive article which make it possible to improve the adhesion with a substrate by a single application.

The solution of the present invention is a polysiloxane adhesive composition, which contains the following components (A) to (F);

(A) an organopolysiloxane having at least two alkenyl-containing organic groups in one molecule,

(B) Contains R ² ₃ SiO _1/2 units and SiO _4/2 units, and the molar ratio represented by (R ² ₃ SiO _1/2 units) / (SiO _4/2 units) is 0.6 to 1.0. Organosiloxane

(C) an organohydrogenpolysiloxane having at least 3 Si-H groups in one molecule,

(D) Platinum group metal catalyst,

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

(F) A silicon compound containing an alkenyl group of 0.15 mol or more in 100 g.

Description

Silicone adhesive composition and adhesive article with excellent substrate adhesion

The invention relates to a polysiloxane adhesive with improved substrate adhesion and an adhesive article.

The so-called adhesive is a kind of adhesive. It is often used in the form of an adhesive tape or an adhesive label that is hardened by applying an adhesive on the substrate. This is a representative of the articles that are commonly used with adhesives. Sex. These items are used to identify items, to be used for luggage bags, or to join multiple items, etc., and they are used for many purposes.

There are several types of base materials used to form adhesives, which are roughly classified into rubber-based, acrylic, and silicone-based. Rubber-based adhesives have been widely used as basic materials since ancient times. They are inexpensive and used in products such as general-purpose tapes. Acrylic adhesives are based on polyacrylates and are used by users. Because of their chemical properties, they are better than rubber-based adhesives. They are also suitable for adhesive products with higher performance than rubber-based adhesives. Polysiloxane adhesive is composed of high viscosity polysiloxane (rubber) and polysiloxane resin. The main chain has many siloxane bonds and has various excellent characteristics. Specific examples include heat resistance, cold resistance, weather resistance, chemical resistance, and electrical insulation.

Polysiloxane adhesives make use of the excellent properties described above. They are used in industrial high-performance tapes such as heat-resistant tapes, masking tapes for engineering, and mica tapes with flame resistance. They are used under severe conditions even under the conditions of use. It can also be used in the case of exhibiting characteristics. However, the demand for polysiloxane adhesives has expanded rapidly in recent years, mainly due to the expansion of the market for products using touch panels equipped on smart phones or tablet terminals. In many cases, a touch panel is directly operated by a human finger, and a screen protection film is used in order to prevent the display from being soiled or damaged. Most of the adhesive layers used in this screen protection film are polysiloxane adhesives, which make use of the characteristics of the polysiloxane adhesive's excellent wettability or rework properties to the adherend.

The base material for the screen protection film is a plastic film, and polyester films such as PET having transparency are often used. However, compared with paper substrates, plastic films can be said to have poor adhesion to adhesives. It is believed that this is because the surface of the plastic film is flat, and the anchoring effect of the adhesive deep into the substrate is weak compared with the paper with large unevenness. If the adhesiveness is poor, there is a problem that the backing occurs when it is taken up by a roll, or the adhesive layer is transferred to the attached body when it is attached to the attached body and peeled off after time has passed.

Conventionally, in order to improve the adhesion, various measures have been taken, such as using a substrate with good adhesion and corona treatment of the substrate. In addition, primer treatment is also a widely performed method. For polysiloxane A primer composition for a coating agent has also been developed (see Patent Documents 1 to 3). Although the primer treatment is very effective, adding one coating step is the biggest disadvantage, and cost and productivity will become a problem. As an effective countermeasure, a method of adding a component having improved adhesiveness to a polysiloxane adhesive and securing the adhesiveness with a single application is considered. Although such additives exist (see Patent Documents 4 to 6), further improvement in adhesion is required. Further, in Patent Document 7, an additive that is selectively attached to an organic resin is described, but the subject is a silicone rubber composition, and there is no mention of a silicone adhesive.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 6-39584

[Patent Document 2] JP 7-3215

[Patent Document 3] JP 2012-149240

[Patent Document 4] JP 2003-105089

[Patent Document 5] Japanese Invention Patent No. 3232004

[Patent Document 6] Special Publication No. 2010-500462

[Patent Document 7] Japanese Invention Patent No. 3324166

Then, the objective of this invention is to provide the polysiloxane adhesive composition which can improve the adhesiveness with a base material by a single application, and Adhesive items.

The present inventors devoted their efforts to the review in order to achieve the above-mentioned objective. As a result, they learned that by adding an adhesion promoter component having a specific structure, a polysiloxane adhesive composition with improved adhesion to the substrate was obtained. invention.

Therefore, the present invention provides the following polysiloxane adhesive composition and adhesive article.

[I]. A polysiloxane adhesive composition comprising the following components (A) to (F); (A) is represented by the following average composition formula (1), and has at least two olefins in one molecule Organic group containing 1007 g of organic polysiloxane containing alkenyl groups of 0.0007 to 0.05 moles: 100 to 40 parts by mass, (In the formula, R ¹ is the same or different kind of monovalent hydrocarbon group having 1 to 10 carbon atoms, at least two of R ¹ are organic groups containing alkenyl groups having 2 to 10 carbon atoms; a is an integer of 2 or more, b Is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, and 50 ≦ a + b + c + d ≦ 15,000); (B) contains R ² ₃ SiO _1/2 units (where, R ² independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms) and an SiO _4/2 unit without (R ² ₃ SiO _1/2 unit) having no aliphatic unsaturated bond. Organic polysiloxanes with a molar ratio of 0.5 to 1.0 represented by / (SiO _4/2 units): 60 to 0 parts by mass, (C) is represented by the following average composition formula (2), and has 1 molecule Organohydrogenpolysiloxanes with at least 3 Si-H groups: The Mo-ratio of the Si-H group is 0.2 to 15 relative to the alkenyl groups of the components (A) and (B), and 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, 0 <e + f ≦ 3) (D) Platinum group metal catalysts obtained by adding and hardening the alkenyl groups of (A) and (B) components and the Si-H groups of (B) by hydrosilylation: Compared with the above (A) to (C) The total amount of ingredients is 1 ~ 500ppm in terms of metal, (E) is 1 Compounds having one or more repeating units represented by the following formula (3) and one or more Si-H groups in the molecule: 0.01 to 10 with respect to the total amount of the components (A) to (C) Mass parts, [Wherein R ⁴ to R ¹¹ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, and X is selected from a divalent organic group represented by the following formula (4) , (Wherein R ¹² to R ¹³ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, and g is an integer of 1 or more); Y is independently 1 to 6 carbon atoms. 6 hydrocarbon group, which may have an ether group in the structure]; (F) a silicon compound containing 0.15 mole or more of an alkenyl group in 100 g: 0.01 to 10 with respect to the total amount of the components (A) to (C) above Parts by mass.

[II]. An adhesive article, which is an adhesive article having a substrate and an adhesive layer formed on at least one side of the substrate, the adhesive layer is formed by coating the polysiloxane adhesive composition on a substrate Hardened on at least one side of the material.

When the polysiloxane adhesive composition obtained by the present invention is applied to a substrate and used, an adhesive article having good adhesion to the substrate can be obtained.

[Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail.

[(A) Ingredient]

(A) is represented by the following average composition formula (1), and has at least two alkenyl-containing organic groups in one molecule, and contains alkenyl groups in 100 g 0.0007 ~ 0.05 mole of organic polysiloxane: 100 ~ 40 parts by mass.

(In the formula, R ¹ is the same or different kind of monovalent hydrocarbon group having 1 to 10 carbon atoms, at least two of R ¹ are organic groups containing alkenyl groups having 2 to 10 carbon atoms; a is an integer of 2 or more, b Is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, and 50 ≦ a + b + c + d ≦ 15,000).

R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms of the same or different species, and at least 2 of R ¹ are alkenyl-containing organic groups having 2 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, and the like, and carbons of such groups Some or all of the hydrogen atoms to which the atoms are bonded may be substituted with a halogen atom or other groups. Examples of the substituent include trifluoromethyl, 3,3,3-trifluoropropyl, and the like. Among these, a saturated aliphatic group or an aromatic group is preferable, and a methyl group and a phenyl group are more preferable.

As the alkenyl group-containing organic group, those having 2 to 10 carbon atoms are preferred, and examples thereof include alkenyl groups such as vinyl, allyl, hexenyl, and octenyl, allyl propyl, and allyl propyl Acrylomethylalkyl groups such as methyl, methacrylomethylpropyl, etc., and cycloalkenylalkyl groups such as methacrylomethylalkyl, cyclohexenylethyl, and alkenyloxy groups such as vinyloxypropyl Alkyl and the like. Among them, vinyl is preferred.

The amount of alkenyl groups contained in (A) is 0.0007 to 0.05 mol, preferably 0.001 to 0.04 mol in 100 g of organic polysiloxane. It is preferably 0.001 to 0.03 moles. If it is smaller than 0.0007 moles, the crosslinking density becomes smaller, and cohesive failure of the adhesive layer may occur. If it is larger than 0.05 moles, the adhesive layer becomes hard, and proper adhesion or adhesion cannot be obtained. Sexual situation.

a is an integer of 2 or more, b is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, 50 ≦ a + b + c + d ≦ 15,000, preferably 200 ≦ a + b + c + d ≦ 12,000. If a + b + c + d is smaller than 50, the cross-linking point becomes too large, and the reactivity may decrease. If it is larger than 15,000, the viscosity of the composition becomes very high, and workability such as difficulty in mixing and mixing may become difficult. Worse.

The component (A) is usually produced by ring-opening polymerization of a cyclic low-molecular-weight siloxane such as octamethylcyclotetrasiloxane using a catalyst, but since the cyclic low-molecular-weight siloxane containing a raw material is contained after polymerization, Preferably, the cyclic low-molecular-weight siloxane is distilled off while passing an inert gas into the reaction product under heating and reduced pressure.

The component (A) includes, but is not limited to, those represented by the following general formula.

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 (where R ^1-1 is the same Or different kinds of alkenyl-containing organic groups, R ^1-2 is the same or different kind of monovalent hydrocarbon group with 1 to 10 carbon atoms, p ≧ 50, q ≧ 1 (however, in the molecule (R ^1-1 R ^{1- 2 When} SiO) q does not have R ^1-1 , q ≧ 2)).

Examples of R ^1-1 and R ^1-2 include those exemplified by R ¹ described above. Furthermore, it is preferably 50 ≦ p ≦ 15,000, more preferably 1 ≦ q ≦ 1,000, and even more preferably 2 ≦ q ≦ 1,000.

The more specific (A) component includes, but is not limited to, those represented by the following general formula. In addition, Me, Vi, and Ph in the following formula each represent a methyl group, a vinyl group, and a phenyl group.

[(B) Ingredient]

Contains R ² ₃ SiO _1/2 units (wherein R ² independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms having no aliphatic unsaturated bond) and SiO _4/2 The unit is an organic polysiloxane having a molar ratio of 0.5 to 1.0 expressed by (R ² ₃ SiO _1/2 unit) / (SiO _4/2 unit). When the Mohr ratio is less than 0.5, there is a possibility that the adhesive force or stickiness may be reduced. When it exceeds 1.0, the adhesive force or the holding force may be lowered. In addition, the above-mentioned mole 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 having no aliphatic unsaturated bond. As the monovalent hydrocarbon group having 1 to 10 carbon atoms, methyl and ethyl are preferred. Alkyl, propyl, butyl and the like having 2 to 6 carbons, alkyl, phenyl, tolyl and the like having 6 to 10 carbons. The alkenyl group having 2 to 6 carbon atoms is preferably a vinyl group, an allyl group, a butenyl group, or the like.

The component (B) may contain a silanol group or a hydrolyzable alkoxy group in addition to R ² , and the content thereof is preferably 0.01 to 4.0% by mass, and more preferably 0.05 to 3.5% by mass of the total mass of the component (B). . If the content is less than 0.01% by mass, the cohesive force of the adhesive may be reduced. If it is more than 4.0% by mass, the viscosity of the adhesive may be reduced. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, and a phenoxy group, and a methoxy group is preferred in use.

(B) A component may use 2 or more types together. In addition, as long as the characteristics of the present invention are not impaired, R ² ₂ SiO _3/2 units and R ² SiO _2/2 units may be contained in (B).

The component (B) can be obtained by performing a condensation reaction in the presence of a catalyst. This is an operation for reacting the hydrolyzable groups present on the surface with each other, and an effect such as improvement of adhesion is expected. As long as a basic catalyst is used, the reaction can be performed at room temperature to reflux, and neutralization can be performed as needed.

Examples of the alkaline catalyst include lithium hydroxide and hydroxide Metal hydroxides of sodium, potassium hydroxide, calcium hydroxide, etc .; carbonates of sodium carbonate, potassium carbonate, etc .; bicarbonates of sodium bicarbonate, potassium bicarbonate, etc .; metal alkane such as sodium methoxide, potassium butoxide, etc. Oxides; organometals such as butyl lithium; potassium silicides; nitrogen compounds such as ammonia, ammonia, methylamine, trimethylamine, triethylamine, etc., preferably ammonia or ammonia. The temperature of the condensation reaction can be performed from room temperature to the reflux temperature of the organic solvent. The reaction time is not particularly limited, but may be 0.5 to 20 hours, and preferably 1 to 16 hours. After the reaction is completed, a neutralizing agent for neutralizing a basic catalyst may be added as necessary. Examples of the neutralizing agent include acid gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, caprylic acid, and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. As an alkaline catalyst, when ammonia gas, ammonia water, or a low-boiling amine compound is used, an inert gas such as nitrogen can be vented and distilled off.

The blending amount of the component (A) is 100 to 40 parts by mass, and the blending amount of the component (B) is 60 to 0 parts by mass, and the component (B) may not be contained. The total of the components (A) and (B) is 100 parts by mass. The mass ratio of the components (A) and (B) is (A) / (B) = 100/0 ~ 40/60. From the point of adhesion when used with a film or tape, it is preferably 100. / 0 ~ 70/30, more preferably 100/0 ~ 80/20, and even more preferably 100/0 ~ 90/10. (B) When the ratio of a component exceeds 60, adhesiveness may worsen.

[(C) component]

An organohydrogenpolysiloxane having at least 3 Si-H groups in one molecule as represented by 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).

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms of R ³ include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, vinyl, allyl, and hexane. Alkenyl groups such as alkenyl, octenyl, and aryl groups such as phenyl. In addition, a part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted by a halogen atom or other groups. Examples include trifluoromethyl, 3,3,3-trifluoropropyl and the like. . 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.

The component (C) may be exemplified by the following general formula (8), but is not limited thereto.

R ²⁵ ₃ Si-O- (R ²⁶ ₂ Si-O) _t- (R ²⁷ HSi-O) _u -SiR ²⁸ ₃ (8) (where R ²⁵ and R ²⁸ each independently represent a carbon number of 1 to 10 R ²⁶ and R ²⁷ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, t is 0 ≦ t ≦ 100, and u is 3 ≦ u ≦ 80).

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms of R ²⁶ and R ²⁷ include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, vinyl, and allyl. Alkenyl, such as alkyl, hexenyl, octenyl, and aryl, such as phenyl. In addition, part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom or other groups. Examples of the substituent include trifluoromethyl, 3,3,3- Trifluoropropyl etc. R ²⁶ and R ^{27 are} preferably a saturated aliphatic group or an aromatic group, and more preferably a methyl group or a phenyl group. R ²⁵ and R ²⁸ are monovalent hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms of R ²⁵ and R ^{28 are} the same as those described above, t is 0 ≦ t ≦ 100, preferably 0 ≦ u ≦ 80 or 0 <u ≦ 80, and u is 3 ≦ u ≦ 80, preferably 5 ≦ u ≦ 70.

T in the general formula (8) satisfies an integer of 0 ≦ t ≦ 100, and preferably 0 ≦ t ≦ 80 or 0 <t ≦ 80. U in the general formula (8) satisfies an integer of 3 ≦ u ≦ 80, and preferably 4 ≦ u ≦ 70.

(C) The component is usually a ring-opening cyclic low-molecular-weight siloxane such as octamethylcyclotetrasiloxane and Si-H-containing siloxane such as tetramethylcyclotetrasiloxane with an acid catalyst. It is produced by polymerization, but since the cyclic low-molecular-weight siloxane containing raw materials is contained after the polymerization, it is preferable to use the cyclic low-molecular-weight silicon while distilling off the cyclic low-molecular-weight silicon while heating and depressurizing the reaction product Oxane

Examples of the specific structure of the component (C) include, but are not limited to, those shown below. In the following formulae, Me each represents a methyl group.

The compounding amount of the component (C) is 0.2 to 15 in terms of the molar ratio (Si-H group / alkenyl group) to the total alkenyl group of the (A) and (B) components. It is preferably used in a range of 0.5 to 10. When it is less than 0.2, the crosslinking density becomes low, and there is a possibility that the cohesive force and the holding force become low. On the other hand, if it exceeds 15, the crosslinking density will become high, and moderate adhesive force and stickiness will not be obtained.

[(D) component]

The component (D) is a platinum group metal catalyst used to harden the alkenyl group (A) and (B) component and the Si-H group (B) by hydrosilylation. Examples of the center metal of the catalyst include platinum, palladium, iridium, rhodium, osmium, ruthenium, and the like, among which platinum is preferred. Examples of the platinum catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol, a reaction product of chloroplatinic acid and an olefin compound, and a reaction product of chloroplatinic acid and vinyl-containing siloxane. Reactants, etc.

The amount of the component (D) is 1 to 500 ppm, and preferably 2 to 450 ppm, based on the total amount of the components (A) to (C). If it is less than 1 ppm, the reaction may be slow and the curing may be insufficient, and various properties such as adhesion or holding force may not be exhibited. If it exceeds 500 ppm, the flexibility of the cured product may be insufficient.

[(E) Ingredient]

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

[Wherein R ⁴ to R ¹¹ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, and X is selected from a divalent organic group represented by the following formula (4) , (Wherein R ¹² to R ¹³ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, and g is an integer of 1 or more); Y is independently 1 to 6 carbon atoms. The hydrocarbon group of 6 may have an ether group in the structure].

In the formula (3), R ⁴ to R ¹¹ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other. Examples of the halogen atom include fluorine, chlorine, and bromine. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, and butyl. Among these, a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms are preferred, and a hydrogen atom and a methyl group are more preferred.

X is a divalent organic group selected from the above formula (4), and R ¹² to R ¹³ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other. Examples of the halogen atom include fluorine, chlorine, and bromine. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, and butyl. Among these, a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms are preferred, and a hydrogen atom and a methyl group are particularly preferred. g is an integer of 1 or more, preferably 1 to 8, and more preferably 1 to 5. When g is larger than 8, since the number of alkyl groups in the repeating unit increases, the adhesion with the substrate may be deteriorated.

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

Further, an ether group may be contained in the molecule, and examples thereof include the following.

Specific examples of the structure of the expression (3) include, but are not limited to, those shown below. Note that Me in the following formula represents a methyl group.

Examples of the Si-H group-containing group include a compound having at least two Si-H groups in one molecule represented by the average composition formula (9) described below, and specifically, it is removed from the following compounds A radical after at least one hydrogen atom (but having at least one Si-H group). (E) Ingredients also It may have a Si-H group-containing group at the molecular terminal.

As (E) component, the following are mentioned, for example, However, It is not limited to these. Z1 and Z2 are 0 to 10, preferably 0 to 4.

(E) The component is a base material adhesion promoter for a silicone curable composition, and is a main component for improving the adhesion between the silicone resin and the substrate. It is considered that the segment of the formula (3) existing in (E) is effective for adhesion of the base material, and it is presumed that the aromatic ring system particularly functions. It is considered that when the base material is plastic, an aromatic ring is also contained in the plastic, and the π electrons of the aromatic rings interact with each other, and the adhesion is improved by a stacking effect. Furthermore, it is believed that a segment having a Si-H group exists near the aromatic ring segment, and the formation of a bond between the Si-H group and a functional group on the surface of the substrate also contributes to the improvement of adhesion.

With respect to 100 parts by mass of the total amount of the components (A) to (C), the compounding amount of the component (E) is 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass. Preferably 0.1 ~ 1 quality Serving. If the blending amount is less than 0.01 parts by mass, a sufficient adhesion-improving effect cannot be obtained. On the other hand, if it exceeds 10 parts by mass, the Si-H group in the polysiloxane adhesive composition increases and adhesion may occur. When the agent is transferred to the attached body.

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

(Wherein R ¹⁴ to R ²¹ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, W is a divalent organic group selected from the following formula (6), Z It 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 hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, and h is an integer of 1 or more).

In the formula (5), R ¹⁴ to R ²¹ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other. Examples of the halogen atom include fluorine, chlorine, and bromine. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, and butyl. Among these, a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms are preferred, and a hydrogen atom and a methyl group are more preferred.

W is a divalent organic group selected from the above formula (6), and R ²² to R ²³ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other. Examples of the halogen atom include fluorine, chlorine, and bromine. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, and butyl. Among these, a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms are preferred, and a hydrogen atom and a methyl group are more preferred. m is an integer of 1 or more, preferably 1 to 8, and more preferably 1 to 5. When m is larger than 8, since the number of alkyl groups in the repeating unit increases, the adhesion with the substrate may be deteriorated.

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

Further, an ether group may be contained in the molecule, and examples thereof include the following.

Specific examples of the component showing the (E1) component include the following, but are not limited thereto. Each of Me in the following formulae represents a methyl group.

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

R ²⁹ _v H _w SiO _{(4-vw) / 2} (9) (wherein R ²⁹ is 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 of R ²⁹ include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, vinyl, and allyl. , Alkenyl such as hexenyl, octenyl, and aryl such as phenyl. In addition, a part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted by a halogen atom or other groups. Examples of the substituent include trifluoromethyl, 3,3,3-tri Fluoropropyl and so on. R ^{29 is} preferably a saturated aliphatic group or an aromatic group, and more preferably a methyl group or a phenyl group.

Examples of the specific structure of the component (E2) include the following, but they are not limited thereto. In the following formulae, Me each represents a methyl group.

(E) is by hydrosilylation of (E1) and (E2) A compound obtained by adding, but this is an addition of the alkenyl group of (E1) and the Si-H group of (E2). At this time, not all of the Si-H groups contained in (E2) are reacted, and at least one or more of them must be left. This is to add the function of the compound of the present invention to the composition when the compound of the present invention is added to the polysiloxane curable composition and used.

Regarding the alkenyl group of (E1) and the Si-H group of (E2), if the respective mole numbers are taken as me1 and me2, the mole ratio during the reaction is 1 <(me2) / (me1) <14, It is preferably 1 <(me2) / (me1) <10, and more preferably 1 <(me2) / (me1) <8. When (me2) / (me1) is less than 1, the Si-H group required for addition does not remain. When (me2) / (me1) is greater than 14, the number of repeating units from (a1) in (A1) is reduced There may be cases where full functions cannot be exerted.

In order to harden the alkenyl group of (E1) with the Si-H group of (E2) and harden it, a platinum group metal catalyst is required. Examples of the central metal include platinum, palladium, iridium, rhodium, osmium, Ruthenium and the like are taken as examples, with platinum being preferred. Examples of the platinum catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol, a reaction product of chloroplatinic acid and an olefin compound, and a reaction product of chloroplatinic acid and vinyl-containing siloxane. Reactants, etc.

The amount of the platinum group catalyst is preferably 0.1 to 200 ppm, more preferably 0.3 to 180 ppm, relative to the total amount of (E1) and (E2). If it is 0.1 ppm or less, the reaction may be slow and inadequate, and if it is 200 ppm or more, the catalyst may remain in the compound due to insufficient catalyst removal after the reaction and the storage stability may deteriorate. condition.

The production of (E) by hydrosilylation of the (E1) alkenyl group and the (E2) Si-H group can be performed by a common method. That is, it is produced by adding (E1) having an alkenyl group and a platinum group catalyst into the reaction vessel, adding (E2) having a Si-H group, and heating and mixing. After completion of the reaction, the impurities were purified by distillation under reduced pressure. In the production, a solvent can be arbitrarily used, and specifically, aromatic hydrocarbon solvents such as toluene and xylene, hexane, heptane, octane, isooctane, decane, cyclohexane, and methylcyclohexane can be used. Aliphatic hydrocarbon solvents such as alkanes, isoalkanes, hydrocarbon solvents such as industrial gasoline, petroleum ether, and solvent oil, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, Ketone solvents such as 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetone acetone, and cyclohexanone.

[(F) component]

100 g of a silicon compound containing an alkenyl group of 0.15 mol or more was contained.

(F) A component is a component which suppresses the increase of the adhesive force with respect to an adherend over time. When the adhesion enhancer (E) is used, the adhesion of the substrate is improved. At the same time, when a silicone curable composition is used as an adhesive for an adhesive article, the adhesion to the adherend increases over time. (F) is effective for suppressing it. The reason for this is presumably that by adding a small amount of an additive with a large amount of vinyl to the base material having a small amount of vinyl in the polysiloxane adhesive, the hardness of the adhesive layer increases due to the increase in the crosslinking density of the entire adhesive layer. It is difficult to penetrate deeply.

(F) The amount of alkenyl groups contained in the component is an organic polysilicon The oxane is 0.15 mol or more per 100 g, preferably 0.18 mol or more, and more preferably 0.20 mol or more. If it is less than 0.15 mol, the effect of suppressing the increase in adhesion becomes weak. The upper limit is not particularly limited, but may be 2.0 mol or less. Moreover, it is preferable to have at least one siloxane bond in one molecule.

The alkenyl group is preferably one having 2 to 10 carbon atoms, and examples thereof include alkenyl groups such as vinyl, allyl, hexenyl, and octenyl, acrylmethyl, propylmethyl, and methyl Acrylofluorenylalkyl such as propylenepropenylpropyl, cyclopropenylalkyl such as methacrylfluorenylalkyl, cycloalkenylalkyl such as cyclohexenylethyl, and alkenyloxyalkyl such as vinyloxypropyl. Among them, vinyl is preferred.

(F) The viscosity (25 ° C) of the component is preferably in the range of 0.1 to 20,000 mPa · s, and more preferably in the range of 1 to 10,000 mPa · s. The viscosity is a value measured by a rotary viscometer.

Examples of the component (F) include a silicon compound represented by the following average composition formula (10) and containing 0.15 mol or more of an alkenyl group in 100 g. In the formula, n is 0.1 to 100, p is 0.1 to 100, and q is 0.01 to 10.

Specific examples of the (F) component include the following, but are not limited thereto. In addition, Me and Vi in the following formula each represent a methyl group and a vinyl group.

The compounding amount of the (F) component is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (C). If it is less than 0.01 parts by mass, the aforementioned effect of suppressing the increase in adhesive force is weakened, and if it is less than 10 parts by mass If there are too many, the hardening property may deteriorate due to too many crosslinking points.

[(G) Ingredient]

(G) A component-based control agent, which is added when a polysiloxane adhesive composition is formulated or coated on a substrate, so that the treatment liquid does not thicken or gelatinize so as not to start an additional reaction before heat curing. The reaction control agent is arranged on the platinum group metal of the additional reaction catalyst to suppress the additional reaction, and the coordination system is detached during heat hardening to exhibit catalytic activity. Any reaction control agent conventionally used in the additional reaction-hardening polysiloxane composition can be used. Specific examples include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol Alcohol, ethynylcyclohexanol (1-ethynyl-1-cyclohexanol), 3-methyl-3-trimethylsilyloxy-1-butyne, 3-methyl-3-trimethylsilane Oxy-1-pentyne, 3,5-dimethyl-3-trimethylsilyloxy-1-hexyne, 1-ethynyl-1-trimethylsilyloxycyclohexane, bis (2 , 2-dimethyl-3-butynyloxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1, 1,3,3-tetramethyl-1,3-divinyldisiloxane, maleate, adipate, and the like.

The blending amount of the (G) control agent is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (C).

[(H) component]

The (H) component is added to the polysiloxane adhesive composition to produce a pendant of the siloxane in the crosslinked network of the composition. Due to the presence of pendant groups of siloxane, the component can achieve the task of suppressing the adhesion of the adherend to increase over time. When a silicone curable composition is used as an adhesive for an adhesive article, the adhesion force to the adherend increases over time, but by using the (H) component, the substrate adheres well, and the adhesion to the substrate can be suppressed. The adhesion of the attached body increases.

Specifically, (H) an organohydrogenpolysiloxane represented by the following average composition formula (7) (but excluding the component (C) described above) may be added.

(In the formula, R ²⁴ is a monovalent hydrocarbon group of the same or different carbon number 1 to 10; i is an integer of 1 or more, j is an integer of 1 or more, k is an integer of 1 or more, and 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, and examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl, and cyclohexyl. Cycloalkyl, vinyl, allyl, hexenyl, octenyl and other alkenyl groups, phenyl and other aryl groups and the like. In addition, a part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted by a halogen atom or other groups. Examples of the substituent include trifluoromethyl, 3,3,3-tri Fluoropropyl and so on. 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, preferably 1 to 3, and more preferably i = 1. An organohydrogenpolysiloxane having a Si-H group only at the molecular end is preferred Alkane is more preferably an organohydrogenpolysiloxane having one Si-H group at the molecular terminal. Based on the foregoing, a component having a crosslinkable Si-H group at the end of the polysiloxane is effective in the (F) component, and a polysiloxane having one Si-H group in one 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 + l + m ≦ 200. When i + j + k + l + m is smaller than 5, the effect of the side group is not fully exerted. When i + j + k + l + m is larger than 500, it occurs because the side group is too long. The side-group molecules are complexed with each other, and the suppression of the increase in adhesion is insufficient.

Specific examples of the structure representing the (H) component include the following, but are not limited thereto. In addition, i-Pr and n-Bu in the following formulae each represent an isopropyl group and an n-butyl group. Q is 4 to 300, preferably 4 to 100, and R is 1 to 10.

The compounding amount of the (H) component is 0.01 to 100 parts by mass, preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C). It is particularly preferably 0.5 to 10 parts by mass. If the blending amount is less than 0.01 parts by mass, the aforementioned effect of suppressing the increase in adhesion will be weakened. If the adding amount is more than 100 parts by mass, the Si-H group in the polysiloxane adhesive composition will increase, which may occur. In the case where the adhesive is transferred to the attached body.

[other] (Solvent)

When all of the aforementioned components are mixed, the viscosity becomes high and handling becomes difficult. Therefore, a solvent for dilution can be arbitrarily added. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatics such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoalkane. Hydrocarbon solvents, hydrocarbon solvents for industrial gasoline, petroleum ether, solvent oil, etc., acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptane Ketone solvents such as ketones, methyl isobutyl ketones, diisobutyl ketones, acetone acetone, cyclohexanone, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, etc. Ester solvents, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, 1,4-di Ether solvents such as alkane, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, 2-butoxyethyl acetate, etc. Solvents with ester and ether moieties, hexamethyldisilazane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris (trimethylsilyloxy) ) Siloxane-based solvents such as methylsilane, tetrakis (trimethylsilyloxy) silane, or mixed solvents thereof. These systems can be used alone or in a suitable combination of two or more.

[Adhesive article]

By coating the above-mentioned polysiloxane composition on at least one surface of the substrate and curing it, an adhesive article having the substrate and an adhesive layer formed on at least one surface of the substrate can be formed.

As the base material for coating the polysiloxane adhesive, paper or plastic plastic film, glass, metal can be selected. Examples of the paper include high-quality paper, coated paper, coated paper, cellophane, polyethylene laminated paper, and kraft paper. Wait. Examples of the plastic film include polyethylene film, polypropylene film, polyester film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polycarbonate film, and polytetrafluoroethylene. Ethylene film, polystyrene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, triethylfluorenyl cellulose film, polyetheretherketone film, polyphenylene sulfide film, etc. The glass is not particularly limited in thickness, kind, and the like, and may be one subjected to chemical strengthening treatment or the like. Moreover, glass fiber is also applicable, and a glass fiber system may be single substance, and a compound with other resin may also be used. Examples of the metal include aluminum foil, copper foil, gold foil, silver foil, and nickel foil.

Among these substrates, the silicone adhesive of the present invention is preferably a plastic film as a substrate. Adhesive tapes or sheets made with various plastic films as substrates can be used for a variety of applications. Examples of the adherend include glass, metal, and plastic. As an adhesive article, it can be used for protective films of various displays, electrical insulating tapes, masking tapes, splicing tapes for electric wires, and adhesion to the skin. Examples of the display include a television receiver, a computer monitor, a portable information terminal monitor, a surveillance monitor, a video camera, a digital camera, a mobile phone, a portable information terminal, a dashboard display of an automobile, and various devices. ‧Equipment‧Instrument panel displays, liquid crystal displays, organic EL displays, automatic ticket machines, cash dispensers, etc. to display characters or signs, various touch panels or flat panel displays (FPDs) for images, etc.

The thickness of the substrate-based substrate film is not particularly limited, but is preferably 1 to 200 μm, and more preferably 5 to 150 μm. In the case of a base film, an adhesive film is obtained, which comprises a base film and Adhesive layer formed by coating the above polysiloxane composition on at least one side and hardening.

In order to improve the adhesion between the substrate and the adhesive layer, a primer-treated, corona-treated, etching-treated, plasma-treated, or sand-blasted treatment can also be used. Corona treatment is preferred. It is also possible to form a primerless layer without performing a primer treatment.

It is preferable to perform surface treatments such as damage prevention, dirt prevention, fingerprint adhesion prevention, anti-glare, anti-reflection, anti-static, and the like on the adhesive layer surface and the opposite surface of the substrate. Each of the above surface treatments may be performed after the adhesive layer is coated on the substrate, or the adhesive layer may be applied after the surface treatment.

Examples of the damage prevention treatment (hard coating treatment) include treatments of hard coating agents such as acrylate-based, polysiloxane-based, oxetane-based, inorganic-based, and organic-inorganic hybrid systems.

Examples of the antifouling treatment include treatment of antifouling agents such as fluorine-based, polysiloxane-based, ceramic-based, and photocatalyst-based agents.

Examples of the antireflection treatment include a wet treatment for coating an antireflection agent such as a fluorine-based or polysiloxane-based agent, or a dry treatment for vapor deposition or sputtering. Examples of the antistatic treatment include treatment of antistatic agents such as surfactants, polysiloxanes, organic borons, conductive polymers, metal oxides, and vapor deposited metals.

As long as the coating method is a well-known coating method, for example, a comma, a coater, a lip coater, a roll coater, a knife coater, a blade coater, a rod coater, and a kiss coater are mentioned , Gravure coater, screen coating, dip coating, casting coating, etc.

The coating amount is not particularly limited, but the thickness of the adhesive layer after curing may be 0.1 to 300 μm, and preferably 0.5 to 200 μm.

Generally, most catalysts are not mixed in polysiloxane adhesives. The catalyst is used before being evenly mixed. The hardening conditions are not limited as long as they are 20 seconds to 10 minutes at 80 to 150 ° C.

The adhesive force of the cured silicone adhesive composition is preferably in the range of 0.01 to 12.0 N / 25 mm, more preferably 0.01 to 10.0 N / 25 mm, and even more preferably 0.01 to 8.0 N / 25 mm. Above 0.01N / 25mm, it is more attached to the body, and below 12.0N / 25mm, it is easy to redo changes.

[Example]

Hereinafter, manufacturing examples, examples, and comparative examples are shown to specifically explain the present invention, but the present invention is not limited to the following examples. Me is methyl, Vi is vinyl, and n-Bu is n-butyl.

[Production Example 1: (E) Component]

In a 500 mL separable flask equipped with a stirring device, a thermometer, a dropping funnel, and a reflux cooling tube, add 1,3,5,7-tetramethylcyclotetrasiloxane 144.3 g (0.6 mol) and toluene 144.3 g, 0.03 g of a toluene solution containing 0.5% by mass of platinum content of 1,3-divinyl-1,1,3,3-tetramethyldisilanium platinum (0) complex, mix and stir, and heat to About 60 ~ 65 ℃. In it, 2,2-bis (4-allyloxyphenyl) was dropped from the dropping funnel 61.7 g (0.2 mol) of propane was heated to about 80-85 ° C. after the dropping was completed, and reacted at this temperature for 1 hour. After the reaction, in order to remove the platinum of the catalyst, 0.3 g of activated carbon was added and mixed for 2 hours, 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 transparent liquid. As a result of the investigation, it can be seen that the mixture is a mixture of the compounds shown below. Among the compounds z1 = 0 to 4, z1 = 2 is the main component.

[Manufacturing example 2]

In a 500 mL separable flask equipped with a stirring device, a thermometer, a dropping funnel, and a reflux cooling tube, add 1,3,5,7-tetramethylcyclotetrasiloxane, 96.2 g (0.4 mol), and toluene 96.2 g, 0.03 g of a toluene solution containing 0.5 mass of platinum content of 1,3-divinyl-1,1,3,3-tetramethyldisilanium platinum (0) complex, mix and stir, and heat to 60 ~ 65 ℃. In it, 2,2-bis (4-allyloxyphenyl) propane was dropped from the dropping funnel 61.7 g (0.2 mol), after the dropping, heat to about 80-85 ° C, and react at this temperature for 2 hours. After the reaction, in order to remove the platinum of the catalyst, 0.3 g of activated carbon was added and mixed for 2 hours, 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 transparent liquid. As a result of the investigation, it was found that the compound was a mixture of the compounds shown in Production Example 1 above, and the compound with z1 = 3 in z1 = 0 to 4 was the main component.

[Comparative Manufacturing Example 1]

In a 500 mL separable flask equipped with a stirring device, a thermometer, a dropping funnel, and a reflux cooling tube, 86.54 g (0.7 mol) of dimethyldimethoxysilane and 52.89 of methylvinyldimethoxysilane were added. g (0.4 mol) and 8.00 g of methanol, dripped from the dropping funnel into a total of 50 ppm of KOH and 100 g of distilled water, and reacted for 2 hours under methanol reflux, and then concentrated under reduced pressure at 60 ° C / 4 hours to obtain Vinyl-containing siloxanes blocked at the ends by silanols or methoxy groups. The compound was obtained by mixing and stirring the obtained oil and 3-glycidoxypropyltrimethoxysilane at a mass ratio of 50/50 at room temperature for about 1 hour.

<Polysiloxane adhesive composition> [Example 1]

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

(B) 60% of non-volatile organic polysiloxane containing Me ₃ SiO _1/2 units and SiO ₂ units, (Me ₃ SiO _1/2 units) / (SiO ₂ units) with a molar ratio of 0.85 10 parts by mass of a toluene solution by mass, (C) 0.29 parts by mass of an organohydrogenpolysiloxane represented by the following average composition formula (c-1),

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

(G) 0.16 parts by mass of ethynylcyclohexanol, and diluted with toluene to obtain a mixture of 60% by mass of the active ingredient.

50 parts by mass of toluene was added to 100 parts by mass of the obtained 60% by mass active ingredient mixture, and (D) 1,3-divinyl-1,1,3,3-tetramethyldisilazane platinum ( 0) 0.5 part by mass of a toluene solution containing 0.5% by mass of platinum as a complex, as the adhesion-improving component of the present invention The (E) component has 2 parts by mass of the compound obtained in Production Example 1, and the viscosity at 25 ° C. represented by the following average composition formula (f-1) as the (F) component is 24.0 mPa · s and 100 g The silicone compound contained 2 parts by mass of 0.53 moles of a silicon compound to produce a polysiloxane adhesive composition.

[Example 2]

Except that the compound obtained in Production Example 1 was 0.5 parts by mass, the silicon compound having a viscosity represented by an average composition formula (f-1) of 24.0 mPa · s and a vinyl group content of 0.53 in 100 g was 0.5 mass A polysiloxane adhesive composition was produced in the same manner as in Example 1 except that the amount was not greater than 1 part.

[Example 3]

Except that the compound obtained in Production Example 1 was 0.4 parts by mass, the silicon compound having a viscosity represented by the average composition formula (f-1) of 24.0 mPa · s and the amount of vinyl contained in 100 g of 0.53 mole was 0.4 mass. A polysiloxane adhesive composition was produced in the same manner as in Example 1 except that the amount was not greater than 1 part.

[Reference example]

A polysiloxane adhesive was produced in the same manner as in Example 3, except that a silicon compound having a viscosity of 24.0 mPa · s and a vinyl group content of 0.53 mol in 100 g was not added, as shown in the average composition formula (f-1). Agent composition Thing.

[Example 4]

Except that the compound obtained in Production Example 1 was 0.3 parts by mass, the silicon compound having a viscosity represented by the average composition formula (f-1) of 24.0 mPa · s and the amount of vinyl contained in 100 g of 0.53 mole was 0.3 mass. A polysiloxane adhesive composition was produced in the same manner as in Example 1 except that the amount was not greater than 1 part.

[Example 5]

Except that the compound obtained in Production Example 1 was 0.2 parts by mass, the silicon compound having a viscosity represented by an average composition formula (f-1) of 24.0 mPa · s and a vinyl group content of 0.53 in 100 g was 0.2 mass A polysiloxane adhesive composition was produced in the same manner as in Example 1 except that the amount was not greater than 1 part.

[Example 6]

The organic hydrogen polysiloxane represented by the average composition formula (c-1) is 0.12 parts by mass, and the organic hydrogen polysiloxane represented by the average composition formula (c-2) is 0.16 parts by mass. The silicon compound obtained in Example 1 was 0.4 parts by mass, the viscosity at 25 ° C. represented by the average composition formula (f-1) was 24.0 mPa · s, and the silicon compound contained in 100 g of 0.53 moles of silicon compound was 0.4 mass. A polysiloxane adhesive composition was produced in the same manner as in Example 1 except that the amount was not greater than 1 part.

[Example 7]

The organic hydrogen polysiloxane represented by the average composition formula (c-1) was changed to 0.46 parts by mass, and the organic hydrogen polysiloxane represented by the average composition formula (c-2) was changed to 0.66 parts by mass. The silicon compound obtained in Example 1 was 0.4 parts by mass, the viscosity at 25 ° C. represented by the average composition formula (f-1) was 24.0 mPa · s, and the silicon compound contained in 100 g of 0.53 moles of silicon compound was 0.4 mass. A polysiloxane adhesive composition was produced in the same manner as in Example 1 except that the amount was not greater than 1 part.

[Example 8]

Except that the compound obtained in Production Example 1 and the compound obtained in Production Example 2 were 0.4 parts by mass, the viscosity at 25 ° C. represented by the average composition formula (f-1) was 24.0 mPa · s, and the amount of vinyl contained in 100 g A polysiloxane adhesive composition was prepared in the same manner as in Example 1 except that the silicon compound having a molar content of 0.53 was changed to 0.4 parts by mass.

[Example 9]

The same as Example 3 except that the silicon compound having a viscosity at 25 ° C. expressed by the average composition formula (f-1) of 24.0 mPa · s and a vinyl compound content of 100 g of 0.53 mol was 0.2 parts by mass. Polysiloxane adhesive composition is produced.

[Example 10]

Except that the viscosity at 25 ° C. expressed by the average composition formula (f-1) was 24.0 mPa · s and the amount of vinyl contained in 100 g was 0.53 mol A polysiloxane adhesive composition was produced in the same manner as in Example 3 except that the silicon compound was changed to 0.8 parts by mass.

[Example 11]

Except not using 0.4 parts by mass of a silicon compound having a viscosity of 24.0 mPa · s at 25 ° C. represented by the average composition formula (f-1) and a vinyl compound content of 0.53 mol in 100 g, 0.2 mass is used instead. A polysiloxane adhesive composition was prepared in the same manner as in Example 3 except that the silicon compound having a vinyl content of 0.86 mol in 100 g was expressed by the following formula (f-2).

[Example 12]

A polysiloxane adhesive composition was produced in the same manner as in Example 11 except that the silicon compound having a vinyl group content of 0.86 mol in 100 g represented by the formula (f-2) was changed to 0.4 parts by mass.

[Example 13]

Except that 0.4 parts by mass of a silicon compound having a viscosity of 24.0 mPa · s represented by the average composition formula (f-1) and a vinyl content of 0.53 mol in 100 g is not used, 0.4 parts by mass of Take the following A polysiloxane adhesive composition was produced in the same manner as in Example 3 except that the silicon compound having a vinyl group content of 0.20 mol in 100 g represented by the formula (f-3).

[Example 14]

A polysiloxane adhesive composition was produced in the same manner as in Example 13 except that the silicon compound having a vinyl group content of 0.20 mol in 100 g represented by the average composition formula (f-3) was 0.8 parts by mass.

[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 an organohydrogenpolysiloxane represented by the following average composition formula (c-1),

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

(G) 0.18 parts by mass of ethynylcyclohexanol, and diluted with toluene to obtain a mixture of 60% by mass of the active ingredient.

50 parts by mass of toluene was added to 100 parts by mass of the obtained mixture, and (D) 1,3-divinyl-1,1,3,3-tetramethyldisiladium platinum (0) complex was added. 0.5 parts by mass of a 0.5% by mass platinum solution in toluene, 0.4 parts by mass of the adhesion promoter described in Production Example 1 of the (E) component as the adhesion promotion component, and 25 by the average composition formula (f-1) A silicone compound having a viscosity of 24.0 mPa · s and a content of 0.43 parts by mass of a silicon compound having a vinyl group content of 0.53 mol at 100 ° C. was prepared.

[Example 16]

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

(B) 60% of non-volatile organic polysiloxane containing Me ₃ SiO _1/2 units and SiO ₂ units, (Me ₃ SiO _1/2 units) / (SiO ₂ units) with a molar ratio of 0.85 20 parts by mass of a toluene solution by mass, (C) 0.26 parts by mass of an organohydrogenpolysiloxane represented by the following average composition formula (c-1),

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

(G) 0.18 parts by mass of ethynylcyclohexanol, and diluted with toluene to obtain a mixture of 60% by mass of the active ingredient.

To 100 parts by mass of the obtained mixture, 50 parts by mass of toluene was added, and (D) 1,3-divinyl-1,1,3,3-tetramethyldisilanium platinum (0) complex was added. 0.5 mass part of a toluene solution containing 0.5 mass% of a platinum content, 0.4 mass part of the adhesion promoter described in Production Example 1 of the (E) component as the adhesion promotion component of the present invention, and an average composition formula (f-1) The indicated viscosity was 24.0 mPa · s, and 0.4 g parts by mass of a silicon compound having a vinyl group content of 0.53 mol in 100 g was used to prepare a polysiloxane adhesive composition.

[Example 17]

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

(B) 60% of non-volatile organic polysiloxane containing Me ₃ SiO _1/2 units and SiO ₂ units, (Me ₃ SiO _1/2 units) / (SiO ₂ units) with a molar ratio of 0.85 40 parts by mass of a toluene solution by mass, (C) 0.19 parts by mass of an organohydrogenpolysiloxane represented by the following average composition formula (b),

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

(G) 0.18 parts by mass of ethynylcyclohexanol, and diluted with toluene to obtain a mixture of 60% by mass of the active ingredient.

50 parts by mass of toluene was added to 100 parts by mass of the obtained mixture, and (D) 1,3-divinyl-1,1,3,3-tetramethyldisilazane platinum (0) was added. 0.5 part by mass of a toluene solution containing 0.5% by mass of a platinum component in a complex, 0.4 part by mass of the adhesion promoter described in Production Example 1 as an adhesion promotion component (E) component, and an average composition formula (f-1 The viscosity at 25 ° C. is 24.0 mPa · s and 0.4 parts by mass of a silicon compound having a vinyl group content of 0.53 mol in 100 g is used to prepare a polysiloxane adhesive composition.

[Example 18]

To the polysiloxane adhesive composition prepared in Example 3, 0.4 parts by mass of an organohydrogenpolysiloxane represented by the average composition formula (h-1) below (H) component was further added to prepare a polysiloxane. Silicone adhesive composition.

[Example 19]

To the polysiloxane adhesive composition prepared in Example 3, 0.4 parts by mass of an organohydrogenpolysiloxane represented by the average composition formula (h-2) below (H) component was further added to prepare a polysiloxane. Silicone adhesive composition.

[Example 20]

To the polysiloxane adhesive composition prepared in Example 3, 0.4 part by mass of the average composition formula (h-3) below the (H) component was further added. The indicated organohydrogenpolysiloxane is used to make a polysiloxane adhesive composition.

[Example 21]

To the polysiloxane adhesive composition prepared in Example 3, 0.4 parts by mass of an organohydrogenpolysiloxane represented by the average composition formula (h-4) below (H) component was further added to prepare a polysiloxane. Silicone adhesive composition.

[Example 22]

A polysiloxane adhesive composition for the test was produced in the same manner as in Example 19 except that 0.8 parts by mass of the organohydrogenpolysiloxane represented by the average composition formula (h-2) was added.

[Comparative Example 1]

Except that the compound obtained in Production Example 1 was not added, and the silicon compound having a viscosity represented by the average composition formula (f-1) of 24.0 mPa · s and the amount of vinyl contained in 100 g of 0.53 mole was not added, A polysiloxane adhesive composition was produced in the same manner as in Example 1.

[Comparative Example 2]

In addition to replacing the compound obtained in Production Example 1 with a silicon compound having a viscosity of 24.0 mPa · s represented by the average composition formula (f-1) and a silicon compound having a vinyl content of 0.53 mol in 100 g, 0.4 parts by mass of A polysiloxane adhesive composition was prepared in the same manner as in Example 1 except for 2,2-bis (4-allyloxyphenyl) propane.

[Comparative Example 3]

It was produced in the same manner as in Comparative Example 2 except that 0.4 parts by mass of a silicon compound having a viscosity represented by an average composition formula (f-1) of 24.0 mPa · s and a vinyl content of 100 g of 0.53 mol was added. Polysiloxane adhesive composition for testing.

[Comparative Example 4]

In addition to replacing the compound obtained in Production Example 1 with a silicon compound having a viscosity of 24.0 mPa · s represented by the average composition formula (f-1) and a silicon compound having a vinyl content of 0.53 mol in 100 g, a comparative production example was used. A polysiloxane adhesive composition was prepared in the same manner as in Example 1 except for the obtained compound.

About the said polysiloxane adhesive composition, the adhesiveness and adhesive force were evaluated by the following method.

<Adhesiveness>

A processing bath was prepared by adding 100 parts by mass of the above-mentioned active ingredient to 60% by mass, adding (D) a curing catalyst, and the components (E) and (F) described above, and rapidly mixing and stirring. A coater was used to set the cured bath. The thickness of the adhesive layer was 30 μm, and the treatment bath was coated on a polyethylene terephthalate (PET) film having a thickness of 23 μm and a width of 25 mm. This was air-dried in a dryer at 130 ° C for 1 minute. After the produced adhesive article was allowed to stand under certain conditions, the adhesive layer was scratched with protrusions such as nails or knives to make scars, and rubbed with a finger belly. This part was evaluated as follows. In addition, the conditions for the stationary adhesive article are four conditions: one day at room temperature, one day at 60 ° C / 90% RH, one day at 85 ° C / 85% RH, and seven days at 60 ° C / 90% RH. . The results are expressed on the following basis.

(Benchmark)

○: The adhesive layer is not peeled from the substrate.

×: The adhesive layer is peeled from the substrate

<Adhesion>

A processing bath was prepared with 100 parts by mass of a mixture of 60% by mass of an active ingredient, a curing catalyst was added and the components (E) and (F) described above were rapidly mixed and stirred, and the thickness after curing was 30 μm, and applied using a coating The processing bath was applied to a polyethylene terephthalate (PET) film having a thickness of 23 μm and a width of 25 mm, and then heated and cured at 130 ° C./1 minute to prepare an adhesive tape. This adhesive tape was affixed to a glass plate, and the roller covered with a rubber layer having a weight of 2 kg was reciprocated twice and pressed. Place the glass plate with the adhesive tape in the constant temperature and humidity bath for a specified number of days, take it out, and use a tensile tester to measure at a speed of 300 mm / min. When the tape is removed from the glass plate at an angle of 180 ° Required force (N / 25mm).

In Examples 1 to 22, it was possible to improve the adhesion to the substrate with a single application, and the substrate adhesion was good under the above four conditions. It is believed that this is manifested by the interaction between the phenyl component of the (E) component and the substrate at the interface due to the π electron stacking effect. If you compare Examples 2 to 14 and 18 to 22 with the reference example, it can be seen that the reference example has a larger increase in adhesion over time. It is believed that this is because it has a phenyl group and interacts with the silanol group on the glass surface. effect. However, by adding (F) component, It is possible to suppress the increase of the adhesive force over time. It is thought that this is because the crosslinking density of the entire adhesive layer is increased, the hardness of the adhesive layer is increased, and the adhesive layer is difficult to hook on the unevenness on the surface of the adherend. In addition, it was found that the (H) component was used in combination to suppress the increase in adhesive force over time while maintaining the adhesiveness of the substrate.

On the other hand, in Comparative Example 1 to which no adhesion enhancer was added, the adhesion cannot be secured. In the case of using Comparative Production Example 1, although the adhesion was ensured only in the initial stage, the adhesion was insufficient over time. In addition, Comparative Examples 2 and 3 using 2,2-bis (4-allyloxyphenyl) propane as a raw material for the component (E) also had insufficient adhesion. The main reason is considered to be that only the raw materials are used. The molecular weight is small, so the interaction with the substrate can only partially function. It is considered that the effects may be exhibited by using those having a large molecular weight as produced in Production Examples 1 and 2. In the measurement of adhesion, the adhesion layer will be transferred to the glass, which also implies insufficient hardening.

Claims (7)

A polysiloxane adhesive composition comprising the following components (A) to (F); (A) is represented by the following average composition formula (1), and has at least two organic groups containing alkenyl groups in one molecule , Organic polysiloxane containing alkenyl groups of 0.0007 to 0.05 moles in 100 g: 40 to 100 parts by mass, (In the formula, R ¹ is the same or different kind of monovalent hydrocarbon group having 1 to 10 carbon atoms, at least two of R ¹ are organic groups containing alkenyl groups having 2 to 10 carbon atoms; a is an integer of 2 or more, b Is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, and 50 ≦ a + b + c + d ≦ 15,000); (B) contains R ² ₃ SiO _1/2 units (where, R ² independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms) and an SiO _4/2 unit without (R ² ₃ SiO _1/2 unit) having no aliphatic unsaturated bond. / (SiO _4/2 units) Organic polysiloxanes with a molar ratio of 0.5 to 1.0: 0 to 60 parts by mass (however, the total of (A) and (B) components is 100 parts by mass); (C) An organohydrogenpolysiloxane having at least 3 Si-H groups in one molecule as represented by the following average composition formula (2): the total amount of alkenyl groups with respect to the components (A) and (B) The Si-H group is a molar ratio of 0.2 to 15, and R ³ _e H _f SiO _{(4-ef) / 2} (2) (where R ³ independently represents an unsubstituted or substituted carbon number of 1 ~ 10 monovalent hydrocarbon group, e> 0, f> 0, 0 <e + f ≦ 3); (D) Alkenyl group for (A) and (B) components and Si-H group for (B) Platinum group metal catalyst hardened by hydrosilylation: The total amount of the components (A) to (C) is 1 to 500 ppm in terms of the amount of metal, and (E) has one or more repeating units represented by the following formula (3) in one molecule and one or more Si-H-based compound: 0.01 to 10 parts by mass relative to 100 parts by mass of the total of the components (A) to (C), [Wherein R ⁴ to R ¹¹ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, and X is selected from a divalent organic group represented by the following formula (4) , (Wherein R ¹² to R ¹³ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, and g is an integer of 1 or more); Y is independently 1 to 6 carbon atoms. Hydrocarbon group of 6 may have an ether group in the structure]; (F) a silicon compound containing 0.15 mol or more of an alkenyl group in 100 g: 100 parts by mass with respect to the total amount of the above components (A) to (C), is 0.01 to 10 parts by mass. For example, the polysiloxane adhesive composition of claim 1 further contains 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 polysiloxane adhesive composition according to claim 1 or 2, wherein the component (E) is an organic compound (E1) represented by the following formula (5) and A compound obtained by adding at least two Si-H-based compounds (E2) to hydrosilylation; (Wherein R ¹⁴ to R ²¹ are hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, W is a divalent organic group selected from the following formula (6), Z It 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 hydrogen atoms, halogen atoms, hydroxyl groups, or monovalent hydrocarbon groups having 1 to 6 carbon atoms which are the same or different from each other, and h is an integer of 1 or more). The polysiloxane adhesive composition according to claim 1 or 2, wherein the component (F) is a silicon compound having at least one siloxane bond in one molecule. The polysiloxane adhesive composition according to claim 1 or 2, further comprising (H) an organohydrogenpolysiloxane represented by the following average composition formula (7) (however, the component (C) is not included) (In the formula, R ²⁴ is a monovalent hydrocarbon group of the same or different carbon number 1 to 10; i is an integer of 1 or more, j is an integer of 1 or more, k is an integer of 1 or more, and l and m are integers of 0 or more And 5 ≦ i + j + k + l + m ≦ 500), and contains 0.01 to 100 parts by mass of (H) with respect to the total amount of the above (A) to (C) components. An adhesive article is an adhesive article having a substrate and an adhesive layer formed on at least one side of the substrate. The adhesive layer is adhered by a polysiloxane as in any one of claims 1 to 5. The agent composition is obtained by coating on at least one side of a substrate and curing it. The adhesive article of claim 6, wherein the substrate is a plastic film.